As emerging pollutants, pharmaceutical and personal care products (PPCPs) have received extensive attention due to their high detection frequency (with concentrations ranging from ng/L to μg/L) and potential risk to aqueous environments and human health. Advanced oxidation processes (AOPs) are effective techniques for the removal of PPCPs from water environments. In AOPs, different types of free radicals (HO·, SO4·−, O2·−, etc.) are generated to decompose PPCPs into non-toxic and small-molecule compounds, finally leading to the decomposition of PPCPs. This review systematically summarizes the features of various AOPs and the removal of PPCPs by different free radicals. The operation conditions and comprehensive performance of different types of free radicals are summarized, and the reaction mechanisms are further revealed. This review will provide a quick understanding of AOPs for later researchers.