It's actually the other way around. That axial rotation of the pions ensures that, given its non-vanishing v.e.v., given by the condensate (assumed to be produced by QCD: a fact!), they therefore must be the Goldstone modes of the SSB of the axial charges. But, first, the chiral condensate is required so as to unleash all this.
Take L=2, for simplicity, and let's be schematic (~) about normalizations, which you may adjust to your satisfaction, in comportance with the conventions of your text. 
Let us consider the relevant fermion bilinears and their representation of the $SU(2)_L\times SU(2)_R$. (By the way, the 3 axial $\vec{Q}_A$ do not close to an SU(2), as you wrote, as their commutators close to $SU(2)_V$ instead. Don't ever write this again... Also, $U(1)_A$ is broken explicitly by the anomaly, not spontaneously.) So, the 4 bilinears, 
$\bar{\psi} {\psi} $, $\bar{\psi}\gamma_{5} \vec{\tau} {\psi} $ form a quartet of this chiral group formally analogous of the $\sigma, \vec{\pi}$ quartet of the σ-model of the 60s; in fact, they are the QCD interpolating fields for this quartet. 
(If you are insouciant about i s and the like, you may think of this scalar-pseudoscalars quartet as a 4-vector $t,\vec{x}$ of the Lorentz group,
as a familiar mnemonic of the combinatorics/groupery to follow: The vector isorotations are analogous to the 3 rotations, and the 3 axials are analogous to the 3 boosts, acting on 4-vectors.)
You then see that
$$
  \left[\vec{Q}_{V},\bar{\psi}\psi\right]=0,
$$
$$
\left[\vec{Q}_{A},\bar{\psi}\psi\right]\sim \bar{\psi} \gamma_{5} \vec{\tau} \psi ~,
$$
$$
  \left[Q_{a}^{V}  ,\bar{\psi} \gamma_{5}\tau_{b} \psi \right] \sim \epsilon _{abc}
\bar{\psi}\gamma_{5}\tau^c\psi ~,
$$
and, crucially, the relation of interest, where you note the $\gamma_{0}\gamma_{5}$ makes all the difference in the combinatorics, as in the σ -model link, above, 
$$
  \left[Q_{a}^{A}  ,\bar{\psi} \gamma_{5}\tau_{b} \psi \right] \sim
  \delta_{ab}  \bar{\psi}\psi ~.
$$
So the σ is an isosinglet; the axials transform the σ by $\vec\pi$s; the vector transform of the  $\vec \pi$s is an isorotation thereof; and the suitable "diagonal" axial transforms of the  $\vec\pi$s takes them to the 
σ, the QCD analog of the Higgs of the EW interactions, the guy with the v.e.v.
Now take the v.e.v. $
\langle \Omega \lvert ... ...  \rvert\Omega \rangle$ of each of the above. 
The r.h.sides of the first 3 must vanish; the v.e.v.s of the Goldstone modes are null!
The v.e.v. of the last one does not, but $=v\approx (250MeV)^3$, your relation of interest. QCD just achieves that, by dint of strong dynamics.  So, over and above making it impossible for the axials to annihilate the vacuum, it identifies the 3 pions as the Goldstone modes of the 3 SSBroken $\vec{Q}_A$. 
In point of fact, you actually see that $\vec{Q}_{A} \rvert\Omega \rangle \sim |\vec{\pi}\rangle$, that is the axial charges pump pions (chiral goldstons) out of the vacuum--- the precursor to PCAC.
A final loose end, lest you might still object that the third relation with vanishing r.h.side would then be moot, $\langle  \vec{\pi} \lvert  \bar{\psi}   \psi \rvert\Omega \rangle=0$; but, no, the pion is orthogonal to the σ, just as it is to the original vacuum "chosen", $\langle  \vec{\pi}  \vert\Omega \rangle=0$. 
(Could insert  $\vert\Omega\rangle \langle\Omega\vert$ above and factor out the order parameter, $\langle  \vec{\pi}   \vert\Omega \rangle v=0$ )
Further related (formally identical) questions might be 281696, and, needless to say, Gell-Mann and Lévy's timeless 1960 σ -model classic.