Let $a,b\in\mathbb N$, and assume we want to prove that the decimal expansion of $b/a$ is eventually periodic. If $a>b$, then there exist unique $q,r\in\mathbb Z$ such that $a=qb+r$ with $0\leq r<b$. so $a/b=q+r/b$. Hence, if we can show that $r/b$ is eventually periodic, we are done. So WLOG assume that $a<b$.
One can prove that we can construct a decimal expansion of $a/b$ satisfying the following properties:
Define a sequence $(r_n)$ recursively, by setting $r_0=$ and
$$
r_n=10 r_{n-1}-d_{n-1}\cdot b
$$
such that $0\leq r_{n-1}<b$ (note that $r_n$ is uniquely determined by the division-with-remainder theorem). Then a decimal expansion of $a/b$ is given by $=\sum_{i\leq -1} d_i 10^i$.
See e.g. §16 in Elementary Analysis by Kenneth Ross.
Using this, and Theorem 16.3 in Ross (which says that each real number has either a unique decimal expansion or two decimal expansions, one ending in a sequence of all $0$'s and the other ending in a sequence of al $9$'s), one can indeed invoke the pigeon principle:
Each $r_{n-1}$ determines $r_n$ uniquely, and there can at most $b+1$ distinct $r_n$. So there exist integers $m$ and $p$ such that $0\leq m<m+p\leq b$ and $r_m=r_{m+p}$. One can then prove inductively that for $k\geq m+1$, $r_k=r_{k+p}$. For the details I refer to Theorem 16.5 in Ross.