Suppose that $a[n]$ is periodic with period $q$. Observe that the $\sum_{m=0}^{n-1} a[m] = \lfloor n\pi \rfloor$, as the sum telescopes. Let $p=\lfloor q\pi \rfloor=\sum_{m=0}^{q-1} a[m]$, so $p$ is an integer. Then for all positive integers $k$,
$\lfloor kq\pi \rfloor=\sum_{m=0}^{kq-1} a[m]=\sum_{i=0}^{k-1} \sum_{j=0}^{q-1} a[qi+j]=\sum_{i=0}^{k-1} \sum_{j=0}^{q-1} a[j]=k \sum_{j=0}^{q-1} a[j]=kp$.
(The third term is obtained by dividing each $m$ in the second term by $q$ with quotient $i$ and remainder $j$). By the definition of $\lfloor x \rfloor$, we have that for all positive integers $k$,
$kp\le kq\pi,
or
$\frac{p}{q}\le \pi<\frac{p}{q}+\frac{1}{kq}$.
Now for any real number $\varepsilon>0$, if we let $M=\lfloor \frac{1}{q\varepsilon} \rfloor+1$, then
$M-1\le\frac{1}{q\varepsilon},
so $\frac{1}{Mq}<\varepsilon$. Thus for all real numbers $\varepsilon>0$,
$\frac{p}{q}\le\pi<\frac{p}{q}+\frac{1}{Mq}<\frac{p}{q}+\varepsilon$,
so $\pi=\frac{p}{q}$. Since $\pi$ is irrational, this is a contradiction, so $a[n]$ must not be periodic.
If you're interested, this argument also proves that $a[n]$ is not periodic if $\pi$ is replace with any irrational number, and it is easy to prove that $a[n]$ is periodic if $\pi$ is replaced with a rational number.