The /TU argument of Raw expects unformatted text. Any citation command is devised to format bibliographic data, so the problem isn't really an issue with biblatex. You can access unformatted data using the biblatex commands \thefield, \thename and \thelist. The latter two return name and literal list fields, respectively. Unfortunately they don't give output suitable for printing.
Below we define the citation commands \tooltipcitefield and \tooltipcitename, which make use of \thefield and \thename. These macros have three arguments to specify the display text, field name and entry keys. If the specified field isn't labelnumber, the fields are prefixed with the label number wrapped in brackets.
\documentclass{article}
\usepackage[american]{babel}
\usepackage{csquotes}
\usepackage[maxcitenames=2]{biblatex}
\usepackage[dvips]{hyperref}
\newcounter{tooltip}
\newcommand*{\tooltip}[2]{%
\pdfmark[#1]{
pdfmark=/ANN,Subtype=/Widget,
Raw={/TU (#2 ) % annotation text
/T (tooltip \thetooltip) % annotation title
/FT /Btn % button field
/Ff 65536 % push button field flag
/H /N % no highlighting
}
}%
\stepcounter{tooltip}}
\makeatletter
\newrobustcmd*{\cbx@displaytext}{}
\newrobustcmd*{\mkbibtooltip}[1]{%
#1\cbx@displaytext%
\settowidth{\@tempdima}{\cbx@displaytext}%
\nobreak\hskip-\@tempdima%
\tooltip{\hskip\@tempdima}{\csuse{cbx@tooltiptext}}%
\csgdef{cbx@tooltiptext}{}}
\DeclareCiteCommand{\cbx@tooltipcitefield}[\mkbibtooltip]
{\iffieldundef{prenote}{}{\BibliographyWarning{Ignoring prenote argument}}}
{\ifcsstring{cbx@field}{labelnumber}
{}
{\csxappto{cbx@tooltiptext}{[\thefield{labelnumber}] }}%
\csxappto{cbx@tooltiptext}{\thefield{\csuse{cbx@field}}}}
{\csgappto{cbx@tooltiptext}{; }}
{\iffieldundef{postnote}{}{\BibliographyWarning{Ignoring postnote argument}}}
\newrobustcmd*{\tooltipcitefield}[2]{%
\renewrobustcmd*{\cbx@displaytext}{#1}%
\csgdef{cbx@field}{#2}%
\cbx@tooltipcitefield}
\DeclareIndexNameFormat{thename}{%
\ifnumgreater{\value{listcount}}{\value{liststart}}
{\ifboolexpr{ test {\ifnumless{\value{listcount}}{\value{liststop}}}
or test \ifmorenames }
{\csgappto{cbx@tooltiptext}{, }}
{\ifnumgreater{\value{liststop}}{2}{\csgappto{cbx@tooltiptext}{,}}{}%
\csgappto{cbx@tooltiptext}{ and }}}
{}%
\ifuseprefix{\ifblank{#5}{}{\csgappto{cbx@tooltiptext}{#5 }}}{}%
\csgappto{cbx@tooltiptext}{#1}%
\ifboolexpr{ test {\ifnumequal{\value{listcount}}{\value{liststop}}}
and test \ifmorenames }
{\ifnumgreater{\value{liststop}}{1}{\csgappto{cbx@tooltiptext}{,}}{}%
\csgappto{cbx@tooltiptext}{ et al.}}
{}}
\DeclareCiteCommand{\cbx@tooltipcitename}[\mkbibtooltip]
{\iffieldundef{prenote}{}{\BibliographyWarning{Ignoring prenote argument}}}
{\csxappto{cbx@tooltiptext}{[\thefield{labelnumber}] }%
\indexnames[thename]{\csuse{cbx@name}}}
{\csgappto{cbx@tooltiptext}{; }}
{\iffieldundef{postnote}{}{\BibliographyWarning{Ignoring postnote argument}}}
\newrobustcmd*{\tooltipcitename}[2]{%
\renewrobustcmd*{\cbx@displaytext}{#1}%
\csgdef{cbx@name}{#2}%
\cbx@tooltipcitename}
\makeatother
\addbibresource{biblatex-examples.bib}
\begin{document}
Filler text \tooltipcitefield{\cite[e.g.][]{bertram,cicero}}{labeltitle}{bertram,cicero}.
Filler text \tooltipcitename{\cites[10--15]{bertram}[10]{cicero}}{labelname}{bertram,cicero}.
\tooltipcitefield{Tooltip titles}{labeltitle}{bertram,companion,cicero}.
\tooltipcitename{Tooltip names}{labelname}{companion,bertram,vangennep}.
\tooltipcitefield{\emph{Tooltip numbers}}{}{cicero,companion}.
\printbibliography
\end{document}
Here's an image of the document taken from Adobe Reader after compiling with latex, bibtex, dvips and ps2pdf.

This solution has a few open problems.
Linebreaks. When the display text breaks across a line, the tooltip is applied only to the text after the linebreak. See the above document for an example.
Hyperlinks and tooltips. These don't combine well. As a workaround the citation commands apply the tooltip to the baseline of the display text. This area is about 3pt high. It can be made higher and be displayed on mouse rollover. Some details on the \pdfmark options can be found on D.P. Story's page.
Citations as display text. With the existing commands you have to specify the entry keys twice. Moreover the tooltip area includes pre- and postnotes and only one tooltip is assigned to citation lists. All of these problems probably can't be addressed with the workaround described above.
Just forgot to add something to the question, perhaps you can help. If I do
– ttonelli Mar 13 '12 at 19:23\tooltipcite{\cite{ctan}}{labeltitle}{ctan}then I get the tooltip, but the hyperref link does not work in the pdf. Is there a simple workaround?dvipsandps2pdf. Using Okular I can see tooltips in the dvi, unless the base text is \cite{} (then the tooltip says "go to page X"); in the pdf I cannot see the tooltips. Now, in Acrobat Reader (which is my goal), I can see the tooltip always, even if I use \cite{} for the base text. But then, the link does not work in Acrobat... – ttonelli Mar 13 '12 at 20:06-latex -draftmode --interaction=nonstopmode file.texand then-bibtex file. The - in front of the commands tells make to ignore the result. – ttonelli Mar 14 '12 at 20:31\settowidthis robust so it won't take any fragile arguments, even if they are protected. The\tooltipcitevariants protect the display text command. This is necessary on the first run. I'll ditch these citation commands in another edit. Regarding the "compromise", your limitation is the driver. Life is much easier withpdflatex. The workflow described in that post is cumbersome, but it is easy to improve. – Audrey Mar 14 '12 at 23:15\tooltipcitevariants so I will keep them, even if I need a workaround on the first run. I tried to use fancytooltips before, but didn't like the way tooltips looked like (I bet there are config options to fix that, but I didn't look much). Anyway, thanks a lot for the help, I wish I could give you more points! – ttonelli Mar 15 '12 at 13:26