NiO is a promising hole transporting material for perovskite solar cells due to its high hole mobility, good stability, easy processibility, and suitable Fermi level for hole extraction. However, the efficiency of NiO-based cells is still limited by the slow hole extraction due to the poor perovskite/NiO interface and the inadequate quality of the two solution-processed material phases. Here, large influences of a monolayer surface modification of NiO nanocrystal layers with ethanolamine molecules are demonstrated on the enhancement of hole extraction/transport and thus the photovoltaic performance. The underlying causes have been revealed by a series of studies, pointing to a favorable dipole layer formed by the molecular adsorption along with the enhanced perovskite crystallization and the improved interface contact. Comparatively, the solar cells based on a diethanolamine-modified NiO layer have achieved a rather high fill factor, indeed one of the highest among NiO-based perovskite solar cells, and high short-circuit photocurrent density (J(sc)), resulting in a power conversion efficiency of approximate to 16%, most importantly, without hysteresis.