Ion pairs between porphyrin-type compounds have been successfully employed for spectral sensitization of semiconductor surfaces and for the preparation of collective binary ionic materials for photonic and (photo)catalytic applications. The understanding of the photophysical processes occurring within ion-paired porphyrin dimers is thus of remarkable importance for the optimization and improvement of such systems. Herein the ion-pair species formed between ZnTMePyP4+ (Zn1) or H2TMePyP4+ (H(2)1) and ZnTPPS4- (Zn2) or H2TPPS4-(H(2)2) in a variety of solvent mixtures are characterized and their photophysics thoroughly investigated by time-resolved techniques. In all the systems studied, very fast and efficient photoinduced charge separation is observed, with the cationic porphyrin being reduced and the anionic one oxidized. Interestingly, despite the very short charge separation distance, the lifetime for charge recombination, depending on the energy gap, can extend into the nanosecond time domain, showing great potential for the utilization of this molecular design within energy conversion schemes.