I'd not use centering here. Anyway, you can do it.
- remove the skip above the display
- move it up one line
Here's with centering and without it.
My preference would be to add explanatory text: what are f and g? Stating the assumptions is very important, in my opinion.
\documentclass{article}
\usepackage{amsmath}
\usepackage{amsthm}
\usepackage{lipsum}% for mock text
\newtheorem{theo}{Theorem}
\newcommand{\asym}[1][]{\underset{#1}{\sim}}
\newcommand{\smallo}[1][]{\underset{#1}{o}}
\newcommand{\notheoremtext}{%
\setlength{\abovedisplayskip}{0pt}%
\mbox{}\vspace{-\baselineskip}%
}
\begin{document}
\lipsum[1][1-4]
\begin{theo}\notheoremtext
\begin{alignat}{3}
f&\asym[\alpha]g
&\quad\Longleftrightarrow\quad & f&=g+\smallo\alpha \
&&\quad\Longleftrightarrow\quad & f&=g+\smallo\alpha
\end{alignat}
\end{theo}
\lipsum[1][1-4]
\begin{theo}
$\begin{alignedat}[t]{3}
f&\asym[\alpha]g
&\quad\Longleftrightarrow\quad & f&=g+\smallo\alpha \
&&\quad\Longleftrightarrow\quad & f&=g+\smallo\alpha
\end{alignedat}$
\end{theo}
\lipsum[1][1-4]
\end{document}

\setlength{\abovedisplayskip}{3pt} \setlength{\belowdisplayskip}{3pt}, or similar. – gernot Jan 21 '21 at 09:29