Sulfur‐centered radicals have a key role in a plethora of synthetic organic transformations, whose scope has been further expanded thanks to the possibility to generate such species under visible light photocatalytic conditions. This review focuses on those transformations involving isocyanides and sulfur‐centered radicals with the aim to highlight the chemical space accessible, both in terms of complexity and diversity, and the mechanistic rational underpinning the current and future development of such chemical methodologies. Sulfur‐centered radicals have a key role in a plethora of synthetic transformations, whose scope is ever‐expanding thanks to visible light photocatalysis. The current review focuses on those transformations involving isocyanides and S‐centered radicals and aims to highlight the chemical space accessible and the mechanistic rational underpinning current and future developments.