Near-infrared (NIR) light control of living cellular activities is a highly desired technique for living cell manipulation because of its advantage of high penetrability towards living tissue. In this study, (π-extended porphyrin)–fullerene linked molecules are designed and synthesized to achieve NIR light control of the membrane potential. A donor–(π-extended porphyrin)–acceptor linked molecule exhibited the formation of the charge-separated state with a relatively long lifetime (0.68 μs) and a moderate quantum yield (27–31%). The hydrophilic trimethylammonium-linked triad molecule successfully altered PC12 cells’ membrane potential via photoinduced intramolecular charge separation.