Aligning equations in a cases environment

I think that you want to use \left\{...\right. around your equation. To be able to align your equations inside these you can use the split environment from the amsmath package.

EDIT

In the comments both above and below the consensus is that the aligned environment is superior to split in this situation. Perhaps I am missing it but I can't see the difference in this example, however, as people more knowledgeable than I are advocating using the aligned environment there must be cases where it does matter.

Here is a comparison of the two environments for this example:

This produces:

\documentclass{article}
\usepackage{amsmath}
\DeclareMathOperator\vol{\text{vol}}
\begin{document}
\[\left\{
  \begin{aligned}
    \pi_n  (i) &= {n^2}/{\vol(G_n)} \cr
    \pi_n (j) &=  {n}/{\vol(G_n)} \cr
    q^{(n)}_{ij} &= {1}/{n^2 } \cr
    q^{(n)}_{ji} &= {1}/{n}
  \end{aligned}\right.\tag{\textbf{aligned}}
\]

\[\left\{
  \begin{split}
    \pi_n  (i) &= {n^2}/{\vol(G_n)} \cr
    \pi_n (j) &=  {n}/{\vol(G_n)} \cr
    q^{(n)}_{ij} &= {1}/{n^2 } \cr
    q^{(n)}_{ji} &= {1}/{n}
  \end{split}\right.\tag{\textbf{split}}
\]

\end{document}