The perovskite ABO3 family demonstrates a wide variety of structural evolutions and physical properties and is arguably the most important family of complex oxides. Chemical substitutions of the A- and/or B-site and modulation of oxygen content can effectively regulate their electronic behaviors and multifunctional performances. In general, the BO6 octahedron represents the main unit controlling the electronic and magnetic properties while the A-site ion is often not involved. However, a series of unconventional perovskite materials have been recently synthesized under high pressure, such as the s-d level controlled Pb-based perovskite family and quadruple perovskite oxides containing transition metal ions at the A-site. In these compounds, the intersite A-B correlations play an important role in electronic behaviors and further induce many emergent physical properties.