An extremely long-lived ( much greater than 8 h) charge-separated species was observed following photoinduced electron transfer in poly(N-vinylcarbazole) coadsorbed with 1,2,4,5-tetracyanobenzene as an electron acceptor on a macroreticular resin, Amberlite XAD-8, at room temperature. The formation and deactivation of the long-lived charge-separated states were discussed from the viewpoints of the effective hole transfer via the carbazolyl groups along the polymer chain to result in the ion pair with rather large interionic distance and the long-distance back electron transfer in the ion pair.