The reversible isomerism of indolinospirobenzopyrans is perhaps among the most studied phenomena in the field of molecular switches. Although they began to gain attention as early as 70 years ago following the seminal work of Hirshberg and Fischer, who were the first to recognize their photochromic behaviours, their implementation as photoacids emerged prominently only in the last decade. In this Review, we contextualize the prerequisites underlying the photo-triggered proton release that occurs in these molecular switches, highlighting the most recent advances in their characterization and application as "metastable-state photoacids" in water.