CsPbX3 perovskite nanocrystals (NCs) have attracted much attention from researchers because of their excellent photoelectric properties like high quantum yield, large absorption cross section, and simple preparation process. The addition of ligands in the synthesis process has a significant effect on the microstructure and photophysical properties of solution-processed NCs, which needs further extensive studies. In this Letter, the effects of ligand electronegativity on the size and photoluminescence (PL) properties of CsPbBr3 NCs were reported. One is typical oleic acid with weak electronegativity, and another is 2-acrylamide-2-methylpropionic sulfonic acid with strong electronegativity. The third is their typical mixture with a molar ratio of 1:1. With the increase in ligand electronegativity, the size of CsPbBr3 NCs increases significantly. However, in contrast to the traditional quantum size confinement effect, the PL peak exhibits an abnormal blue shift gradually and the ligand passivation effect on NC surface defects also becomes more significant. The physical mechanism of this anomalous PL shift phenomena of CsPbBr3 NCs was investigated using the time-resolved PL spectrum and transient absorption spectrum.