Novel types of binding motives have been investigated within the context of sensitizing ZnO-based dye-sensitized solar cells with metalloporphyrins In particular, a complementary class of metalloporphyrin has been synthesized to probe the impact of a face-to-edge/orthogonal versus face-to-face/parallel orientation of the metalloporphyrin with respect to ZnO and has been compared to TiO2-based dye-sensitized solar cells Our studies provide a deep and detailed understanding of the individual electron-transfer processes at the ZnO/metalloporphyrin interface, that is electron injection, recombination, and dye regeneration, by means of steady-state and time-resolved techniques Interestingly, we found that for our novel ZnO/metalloporphyrin systems, the injection efficiencies are close to unity, despite their long, nonconjugated anchoring group length