High-efficiency hole transport layer free perovskite solar cells (HTL-free PSCs) with economical and simplified device structure can greatly facilitate the commercialization of PSCs. However, eliminating the key HTL in PSCs results usually in a severe efficiency loss and poor carrier transfer due to the energy-level mismatching at the indium tin oxide (ITO)/perovskite interface. In this study, we solve this issue by introducing an organic monomolecular layer (ML) to raise the effective work function of ITO with the assistance of an interface dipole created by Sn-N bonds. The energy-level alignment at the ITO/perovskite interface is optimized with a barrier-free contact, which favors efficient charge transfer and suppressed nonradiative carrier recombination. The HTL-free PSCs based on the ML-modified ITO yield an efficiency of 19.4%, much higher than those of HTL-free PSCs on bare ITO (10.26%), comparable to state-of-the-art PSCs with a HTL. This study provides an in-depth understanding of the mechanism of interfacial energy-level alignment and facilitates the design of advanced interfacial materials for simplified and efficient PSC devices.