The importance of the perovskite family spans many fields of science including solid state inorganic chemistry, condensed matter physics, materials science, and geology. Perovskites have such widespread relevance because of their compositional and structural flexibility. Substitutions on both cation and anion sites can be exploited to create a wide variety of compounds with common structural characteristics. Subtle distortions of the basic crystal structure can and do have significant impact on the physical properties. In this talk I will discuss our efforts to understand and predict crystal structures of perovskites. The interplay between octahedral tilting distortions, Jahn-Teller distortions of the octahedra, B-site cation ordering and A-site cation ordering will be examined. I will describe our efforts to prepare and study new complex perovskites. Materials systems that will be discussed include oxynitride perovskites, a new family of quintinary AA’BB’O6 perovskites possessing simultaneous layered ordering of A-site cations and rock salt ordering of B-site cations, and other complex perovskites as time permits. For all systems the discussion will focus on manipulation of structure and bonding interactions to influence electrical and magnetic properties.