Simultaneous thiolation/pyridinylation of alkenes was achieved in a three‐component reaction under visible‐light‐induced conditions. By employing 4CzIPN as a photocatalyst and DIPEA as a base, a variety of alkenes and cyanopyridines reacted well with thioacetates or thiosulfonates to obtain the difunctionalized products in excellent yields with high regio‐selectivity. The thiolation/pyridinylation products could easily transfer to 4‐(1‐phenylvinyl)pyridine or dithioperoxoate compounds. Furthermore, the in vitro antitumor activities of selected compounds were screened through MTT assay and the results showed that compound 6f exhibited similar antitumor activity with 5‐fluorouracil (5‐FU).