Advances in radiotherapy technology during the last 25 years have significantly improved both dose conformation to tumors and the preservation of healthy tissues, achieving almost real-time feedback by means of high-precision treatments and theranostics. Owing to this, developing high-performance systems capable of coping with the challenging requirements of modern ionizing radiation is a key issue to overcome the limitations of traditional dosimeters. In this regard, a deep understanding of the physicochemical basis of gel dosimetry, as one of the most promising tools for the evaluation of 3D high-spatial-resolution dose distributions, represents the starting point for developing new and innovative systems. This review aims to contribute thorough descriptions of the chemical processes and interactions that condition gel dosimetry outputs, often phenomenologically addressed, and particularly formulations reported since 2017.