A series of BiFeO3 nanopowders were prepared by the sol-gel process. X-ray diffraction analysis shows that their rhombohedral crystal symmetry remains unchanged. However, as the particle size decreases, the edge length of the unit cell increases markedly and the angle between the edges deviates increasingly from 60°. Magnetic measurements show obvious weak ferromagnetism. The magnetization and magnetic susceptibility increase with decreasing particle size. Mössbauer studies reveal that the spin canting angles in the smaller particles are bigger and have a wider distribution. The magnetic structure in these particles is a complicated uncompensated antiferromagnetic spin arrangement.