Let $R$ be a finite commutative ring. The unitary Cayley graph of $R$, denoted $G_R$, is the graph with vertex set $R$ and edge set $\left\{\{a,b\}:a,b\in R, a-b\in R^\times\right\}$, where $R^\times$ is the set of units of $R$. An $r$-regular graph is Ramanujan if the absolute value of every eigenvalue of it other than $\pm r$ is at most $2\sqrt{r-1}$. In this paper we give a necessary and sufficient condition for $G_R$ to be Ramanujan, and a necessary and sufficient condition for the complement of $G_R$ to be Ramanujan. We also determine the energy of the line graph of $G_R$, and compute the spectral moments of $G_R$ and its line graph.