An organocatalytic photoinduced 1,2-carbofunctionalization strategy for conjugated dienes has been developed. No exogenous photocatalyst or additives are required in this mild protocol and it allows for highly regioselective and efficient 1,2-carboisothiocyanation through the coupling of a diene, an alkyl radical and TMSNCS. The reaction is proposed to proceed through EDA complexation between the diene and TMSNCS.