A structureproperty relationship in all-organic dye solar cells is revealed by first-principles molecular dynamics and real-time time-dependent density functional theory simulations, accompanied with experimental confirmation. An important structural feature at the interface, TiN anchoring, for a broad group of all-organic dyes on TiO2 is inferred from energetics, vibrational recognition, and electronic data. This fact is contrary to the usual assumption; however, it optimizes electronic level alignment and photoelectron injection dynamics, greatly contributing to the observed efficiency improvement in all-organic cyanoacrylate dye sensitized solar cells.