My MWE:
\documentclass{report}
\usepackage{amsmath}
\begin{document}
\begin{align}
&u = \frac{1}{\theta_{2,3}} \left [ -z_1 - \left ( c_2 + \frac{\epsilon}{2} \right )z_2 - \theta_{2,1}\sin(x_1) - \hat{\theta}_{2,2}x_2 + \dot{\alpha}_1 \right ] \\
&\dot{\xi}_{2,2} = - \frac{\partial \beta_2}{\partial x_2}\left [ \theta_{2,1}\sin(x_1)+\left ( \xi_{2,2} + \beta_2(x_2) \right ) x_2 + \theta_{2,3}u \right ] \\
&\hat{\theta}_{2,2} = \xi_{2,2} + \beta_2(x_2) \\
&\beta_2 = \frac{\gamma}{2}x_2^2
\end{align}
\end{document}
The result:

What I want:

That is, next to the left alignment, I want to align the equal signs of equations (2) to (4).

alignalways aligns with the left-hand side aligned to the right before the sign of relation. you'd be better off usingalignat, for which you need to explicitly indicate where you want spacing. – barbara beeton Aug 06 '14 at 17:21