I want to use unicode character 2259 "estimates" in my document, but cannot find it in the symbols-a4 list or via detexify.
It looks exactly like this: ≙
The closest I get is \triangleq: ≜, but it has a different meaning.
Use \overset from amsmath:
\documentclass{article}
\usepackage{amsmath}
\newcommand{\estimates}{\overset{\scriptscriptstyle\wedge}{=}}
\begin{document}
$A\estimates B$
\end{document}
It won't work in sub/superscripts, but I don't think you need the symbol there.

A different realization is with
\newcommand{\estimates}{\mathrel{\hat{=}}}
that would produce

With the package fontspec, you may call each symbol by its unicode. In this case, the command would be $\symbol{"2259}$. You just have to look for fonts, which are giving you this symbol.
Here are 4 examples:
% arara: lualatex
\documentclass{article}
\usepackage{unicode-math}
\usepackage{booktabs}
\usepackage{fontspec}
\begin{document}
\begin{tabular}{ll}
\toprule
Example & Font\\ \midrule
$a\wedgeq b$ & Latin Modern Math\\
\setmathfont{xits-math}$a\wedgeq b$ & XITS Math\\
\setmathfont{asana-math}$a\wedgeq b$ & Asana Math\\
\setmathfont{texgyrepagella-math}$a\wedgeq b$ & TeX Gyre Pagella Math\\
\bottomrule
\end{tabular}
\end{document}

You can use STIX fonts if you don't mind.
\documentclass{article}
\usepackage{stix} % (Times style) Main fonts of the document will be changed
\begin{document}
$a \wedgeq b$
\end{document}
\stackrel etc., although that isn't perfect.
– Leo Liu
Jun 27 '14 at 12:58
There are several packages listed in symbols-a4 that provide this command as \corresponds.
$\stackrel{\wedge}{=}$? – pablos Jun 27 '14 at 03:14cannot find it in the symbols-a4 list or via detexify, so in this case a valid answer would be how to find the symbol in symbol-a4 or detexify or how to build it otherwise, see given answers. It is no duplicate IMHO – Mensch Aug 12 '19 at 20:31symbols-a4). Detexify would not always be accurate, and I'm not sure how often it is updated. For example,\correspondsmay have been added recently (or more recent than what is loaded in Detexify). – Werner Aug 12 '19 at 20:36