Photocatalysis is one of the effective approaches to solve the energy and environmental problems. In the process of photocatalytic reaction, the catalysts structures, surfaces, and interfaces as well as the defects are the key factors affecting their catalytic efficiency, which can be precisely adjusted by optimizing the synthesis method and enhancing the specific performance. Different from the conventional heat transfer type heating modes, microwave-assisted synthesis is an improved strategy for synthesizing micro- and nano-materials based on the heating mechanisms such as dipole polarization, ionic conduction, conduction loss, and hysteresis loss.This method has some advantages like fast heating, uniform thermal effect and good reproducibility in the thermal synthesis of photocatalytic materials. The pointed heating and directional assembly can be induced by the specific thermal effect under microwave irradiation. Microwave-assisted synthesis has attracted wide attention. This review mainly summarized recent research progress on the microwave photocatalysts synthesis, focusing on the superhot interaction between microwave and condensed matter in the synthesis process. It is indicated that the photocatalytic performance can be enhanced through the optimization of structures, surfaces, and interfaces as well as defects of photocatalysts synthesized in microwave-assisted synthesis method.