In recent times, desulfonylative radical-cross-coupling (RCC) has come to the forefront in synthetic organic, bio, and material chemistry as a powerful strategy to forge C-C and C-heteroatom bonds. Diverse functionalization through metal and photoredox-catalyzed desulfonylation reactions has attracted the scientific community due to the mild reaction conditions, wide functional group tolerance and excellent synthetic efficacy. In this review, we have highlighted the photoredox-mediated desulfonylation reactions developed in the last two decades. The current review will summarize the newly reported methodologies, with particular emphasis on their mechanistic aspects and selectivity issues which have paved a new way towards sustainable CC and CX (X= H or, heteroatom) bond formation.