In this paper, we study new Cayley graphs over the additive group of Galois rings. First we prove that they are expander graphs by using a Weil-Carlitz-Uchiyama type estimation of character sums for Galois rings. We also show that Cayley graphs from Galois rings of characteristic 4 form a new infinite family of Ramanujan graphs by an elementary eigenvalue estimation. Moreover some other spectral properties of our graphs are also discussed.