Herein, we demonstrate for the first time that coumarins derived from [2.2]paracyclophane (pCp) can act as effective organo-photocatalysts and promote the reductive cleavage of sulfonamides under light-irradiation. In the presence of these original compounds, photodesulfonylation reactions occur under mild conditions at low catalyst loadings in the presence of Hantzsch ester. Theoretical and experimental investigations are described, which elucidate the reaction mechanism and the nature of the active species involved in the photocatalytic process. This proof-of-concept study paves the way for further application of pCps in the field of photocatalysis.