In this study, the injection efficiencies and photovoltaic device performances for two different phthalocyanine sensitisers—a Zn(II)Pc (TT-1) and a Ru(II)Pc (TT-35) in dye sensitized photoelectrochemical solar cells were compared. These dyes have similar structures and energetics, but differ significantly in their photophysics, with TT-1 exhibiting a reasonably long lived singlet state, whilst TT-35 exhibits rapid intersystem crossing to a long lived triplet state. Time correlated single photon counting (TCSPC) approach and incident photon conversion efficiency (IPCE) measurements were applied to study the injection efficiency of these two Pc dyes. A comparison of the injection efficiency determined by the two independent techniques, TCSPC and IPCE analysis, shows a good agreement. TT-35 shows higher injection efficiency in comparison to TT-1. This result is consistent with the relative energy and lifetime of the TT-35 triplet state compared to the TT-1 singlet excited state. The high injection efficiency and the long electron diffusion length shown by TT-35 make this dye an interesting red absorbing sensitizer for dye solar cells.