Three-layer Aurivillius ceramics Bi2SrCaNb2TiO12, Bi2Sr1.5Ca.5Nb2TiO12, Bi2Sr2Nb2TiO12, Bi2Sr1.5Ba.5Nb2TiO12, Bi2SrBaNb2TiO12 were formed via solid-state synthesis and their structures characterized by Rietveld analysis of powder x-ray diffraction data. Site mixing was observed for all species with the largest amount of mixing occurring in Bi2SrBaNb2TiO12. Bond valence sum calculations (BVS) showed that the A-site BVS increased from underbonded in the Bi2SrCaNb2TiO12 composition to overbonded in Bi2SrBaNb2TiO12. The A-site BVS increased linearly with lattice parameter and average A-site cation radius. Bi-site position relaxation was observed as the average size of the alkaline earth cation on the Bi-site increased. Site mixing occurs in these compounds in order to relieve interlayer strain between the (Bi2O2)2+ layer and the perovskite blocks, between the Nb and Ti-layers of the perovskite blocks, and to reduce the BVS of the perovskite A-site.