I would like to align the \Longleftrightarrow's with each other, such that the second one is in the same vertical space as the first one, and to not tamper with the aligning of the equal signs (the equals sign in the line with the second \Longleftrightarrow isn't in question).
I'm not sure how to use the ampersands to align both, but in two different places.
\begin{split}
a^a = b^b \Longleftrightarrow a & = \log_a{b^b} \\
& = b\log_a{b}. \\
& = \frac{b\ln b}{\ln a} \\
\Longleftrightarrow a\ln a = b\ln b.
\end{split}
\Longleftrightarrow a&\ln a...
it would solve your problem. Also, next time it would be easier to help you if you don't put a code snippet, but rather, a full Minimal Working Example from\documentclass{
to\end{document}