A porphyrin-quaterthiophene-fullerene triad, in which the center of the quaterthiophene spacer is additionally bridged with a crown ether chain in a sash manner (abbreviated as H2P-(2T(crown)2T)-CM), has been newly synthesized. Photoinduced charge-separation (CS) and charge-recombination processes in the absence and presence of Na+ have been investigated by time-resolved fluorescence and transient absorption spectroscopic methods. Upon photo-excitation of H2P-(2T(crown)2T)-C60 in benzonitrile, CS via 1H2P* generating H 2P*+-2T(crown)2T-C60*- took place, followed by a hole shift to a more energetically stable H 2P-(2T(crown)2T)*+-C60* -. In the presence of Na+, such CS process was completely suppressed by the formation of the Na+-inclusion complex H 2P-(2T(crown-Na+)2T)-C60. Extraction of Na + with the external 15-crown-ether-5 recovered the photoinduced CS process. This result indicates that H2P-(2T(crown)2T)-C60) is an unique photo-switchable system, because (2T(crown)2T) acts as ion-responsible molecular wire. Copyright The Electrochemical Society.