Femtosecond transient absorption spectroscopy (fs-TAS) is a powerful technique for monitoring the electron transfer kinetics in photocatalysis. Several important works have successfully elucidated the electron transfer mechanism in heterojunction photocatalysts (HPs) using fs-TAS measurements, and thus a timely summary of recent advances is essential. This feature article starts with a thorough interpretation of the operating principle of fs-TAS equipment, and the fundamentals of the fs-TAS spectra. Subsequently, the applications of fs-TAS in analyzing the dynamics of photogenerated carriers in semiconductor/metal HPs, semiconductor/carbon HPs, semiconductor/semiconductor HPs, and multicomponent HPs are discussed in sequence. Finally, the significance of fs-TAS in revealing the ultrafast interfacial electron transfer process in HPs is summarized, and further research on the applications of fs-TAS in photocatalysis is proposed. This feature article will provide deep insight into the mechanism of the enhanced photocatalytic performance of HPs from the perspective of electron transfer kinetics.