Photoredox chemical reactions induced by visible light have undergone a renaissance in recent years. Polypyridyl dyes such as Ir(ppy)3 and Ru(bpy)3 are key catalysts in this event, and blue‐ or white‐light irradiation is required for the chemical transformations. However, it remains a challenge to achieve reactions under the lower energy of red light. We disclose, herein, that trifluoroethoxy‐coated subphthalocyanine realizes the red‐light‐driven trifluoromethylation of alkenes and alkynes with trifluoromethyl iodide in good‐to‐high yields. Perfluoroalkylations were also achieved under red light. The reaction mechanism is discussed with the support of UV/Vis spectroscopy and cyclic voltammetry of trifluoroethoxy‐coated subphthalocyanine. Light irradiation/dark study also supports the proposed mechanism.

An eccentric trans-SF4 unit achieves a rod-like linear connection of two independent N-heterocycles, pyridines and triazoles.