The present investigation reports on the preparation of BiFeO3 nanopowders by a sol-gel method using acetylacetone as a stabilizer. Single-phase BiFeO3 nanopowders without any impurity or amorphous phases were obtained when the precursor was thermal treated at temperatures as low as 400 oC for 2 h. Acetylacetone (acac) plays an important role on lowering the formation temperature of pure phase BiFeO3 nanopowders. It is found that Bi/acac molar ratio of 1/30 was favorable for a stable sol and for the lowest crystallization temperature of pure BiFeO3 nanopowders. X-ray diffraction and Fourier transform infrared spectroscopy revealed that thermally induced crystallization process of BiFeO3 nanopowders from Bi-Fe polymeric precursor. When the thermal treated temperature was below 200 oC, only amorphous phase existed. With the temperature increasing up to 300 oC, crystallized phase, carbonate, were detected. After annealed at 400 oC, Bi-Fe precursor totally changed to rhombohedral BiFeO3 nanopowders. Scanning electron microscopy characterized morphologies of BiFeO3 nanopowders calcined at 400 oC and 500 oC. The ferroelectric transition of BiFeO3 nanopowders at 827 oC has been detected by differential thermal analysis.