The thiol–ene reaction leading to a series of thioether derivatives by simple metal and oxidant free visible light promoted photosensitized protocol, following anti‐Markonikov hydrothiolation of unactivated aryl and alkyl olefins at room temperature is demonstrated. Benzil served as a green photosensitizer in this reaction and white LED lights as a light source. This radical based thiol–ene reaction is operationally simple and tolerates a wide variety of functional groups present in olefins.