Photocatalysis is a promising sustainable method to generate solar fuels for the future, as well as having other applications such as water/air purification. However, the performance of photocatalysts is often limited by poor charge carrier dynamics. To improve charge carrier dynamics, it is necessary to characterize and understand charge carrier behavior in photocatalytic systems. This critical review will present Transient Absorption Spectroscopy (TAS) as a useful technique for understanding the behavior of photoexcited charges in semiconductor photocatalysts. The role of TAS amongst other techniques for characterizing charge carrier behavior will be outlined. Basic principles behind TAS will be introduced, and interpretation of TAS spectra and kinetics will be discussed in the context of exemplar literature. It will be demonstrated that TAS is a powerful technique to obtain fundamental understanding of the behavior of photoexcited charges.