The simple and efficient conversion of carboxylic acids into structurally diverse organic molecules is highly desirable in chemical synthesis. This review covers recent developments in photocatalytic methodology for late-stage transformations of complex carboxylic acids and their derivatives enabled by radical decarboxylation and deoxygenation, highlighting some representative and significant contributions in this field. These advancements are categorized based on the reactivity patterns exhibited by the carboxylic acids. Several activation modes to generate alkyl or aryl radical intermediates during decarboxylation of carboxylic acids are presented, namely, single-electron transfer (SET) oxidation, ligand-to-metal charge transfer (LMCT), SET reduction, and energy transfer (EnT) processes. On the other hand, direct activation of C-O bonds in carboxylic acids mediated by phosphoranyl radicals has been discussed and illustrates their potential synthetic application for the synthesis of complex aldehydes, ketones and amides.