ZnO nanopowders were prepared by the sol-gel techniques with two kinds of solvent. Microstructure of powder samples was examined by XRD and TEM. The results indicate that the two ZnO samples have the same crystal and energy band structure. Their photoluminescence (PL) spectra in ultraviolet region are analogous, but their photoluminescence (PL) spectra in visible region are different. The reason is that the two kinds of solvent with different polarity result in the difference in configuration and distribution of the sample surface states in the two systems.