ZnO nanoparticles were synthesized by a sol–gel calcination process following being annealed in air at 400, 600, 800 and 1000°C. X-ray diffraction pattern and X-ray photoelectron spectroscopy show that all the samples present a typical wurtzite structure and no other impurity phases are observed. Room-temperature ferromagnetism from all the samples is confirmed by the vibrating sample magnetometer measurements, which shows that the RTFM decreases with the annealing temperature increasing from 400 to 800°C, and then became larger for the sample annealed at 1000°C. According to the Raman scattering spectra and electron paramagnetic resonance, the RTFM of samples annealed at 600, 800 and 1000°C might be related to the oxygen vacancy related defects. However, the RTFM from the sample annealed at 400°C, presenting nearly the same value as that of the sample annealed at 1000°C, could originate with the interstitial zinc defects associated with XPS and photoluminescence analyses.