It is of great importance to study the selective oxidation of light alkanes on metal oxide catalysts from a fundamental and industrial point of view. Clarification of the relationship between the structure of the oxide catalysts and their catalytic properties is vital for the design of efficient catalysts and for the realization of efficient oxidative conversion of light alkanes. In this review, we summarize some recent progress in the understanding of the structures and catalytic properties of several catalysts including V-P-O, V-Sb-O, Mo-V-Te-Nb-O, and V-Mg-O metal oxides. These oxides as well as the Re-Sb-O catalysts developed by us have been extensively studied for the selective oxidation of light alkanes. We then revisit several key aspects including multi-functionality, site isolation, and phase cooperation. These aspects are required for catalysts that are efficient in the selective oxidation of light alkanes and will provide insights into the design and synthesis of metal oxide catalysts and their efficient application to the oxidative conversion of light alkanes.