Well-dispersed ZnO nanomaterials were synthesized by direct calcination of zinc stearate. Results from Fourier transform infrared (FT-IR) spectra and X-ray diffraction (XRD) indicated both the decomposition degree of organic ligand and the purity of calcined products were increased with the calcination temperature. The influence of decomposition temperature on the morphology of ZnO nanomaterials was investigated by field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The experimental results revealed the morphology of ZnO transformed from nanosheets to hexagonal nanopyramids and then to nanoparticles at 573, 673 and 773 K respectively. Finally, a morphology evolution model of ZnO nanomaterials under different temperatures was proposed.