This study proposes a green and efficient atom- and step-economical method for converting hazardous CS2 to dithiocarbamate derivatives under visible light irradiation and catalyst-free conditions. By the construction of novel C-S and C-N bonds, a series of β-dicarbonyl compounds and amines are incorporated into the products. Under light, CS2 and amine first form bis(dialkylaminethiocarbonyl)disulfides, which then react with K2CO3-activated β-dicarbonyl compounds to form electron donor-acceptor (EDA) complexes and subsequently generate the target products. This study confirms for the first time that bis(dialkylaminethiocarbonyl)disulfides can act as electron acceptors to form an EDA complex with β-dicarbonyl compounds, which are then coupled to form the target product under light.