Abstract The hydrofunctionalization of 1,3‐dienes is a challenging task especially with respect to controlling the regioselectivity of the corresponding adducts. Although various hydrofunctionalization approaches have already been developed, nucleophiles are often unselectively introduced at the C1‐ and C2‐positions of 1,3‐dienes. Here, we report a new methodology for the photocatalytic regioselective hydrofunctionalization of 1,4‐diaryl‐1,3‐butadienes in the presence of a photocatalyst under blue LED irradiation. O ‐, N ‐, and C ‐nucleophiles are regioselectively introduced at the C1‐position of 1,4‐diaryl‐1,3‐butadienes to furnish the corresponding allylic (1,4‐adducts) and homoallylic (1,2‐adducts) derivatives as the major products. Moreover, the resultant mixture of 1,4‐adducts and 1,2‐adducts can be convergently transformed into a single reduced compound via hydrogenation.