Abstract: Complex perovskite oxides exhibit extremely rich physical properties in terms of magnetism, electrical transport, and electrical polarization characteristics due to the competition and coupling of many degrees of freedom. The B-site ions and O ions in perovskite form six-coordinated octahedral units, which are connected at a common vertex toward the basic framework of the perovskite oxide, providing a crucial platform to tailor physical properties. The rotation or distortion of the oxygen octahedra will tip the competing balance, leading to many emergent ground states. To further clarify the subtle relationship between emergent properties and oxide octahedral behavior, this article reviews the structure of perovskite oxides, the characterization methods of oxygen octahedral rotation and the response of transport, electrical polarization and magnetism of several typical perovskite heterostructures to oxygen octahedral rotation modes. With knowledge of how to manipulate the octahedral rotation behavior and regulate the physical properties of perovskite oxides, rationally designing the sample manufacturing process can effectively guide the development and application of novel electronic functional materials and devices.