We report on the magnetic anisotropic properties of pure and Mg doped LiFePO4 single crystals grown by the traveling solvent floating zone technique. Our results reveal a considerable anisotropy in the susceptibilities along H‖a, H‖b, and H‖c for both crystals. LiFePO4 and Li0.99Mg0.01FePO4 crystals show antiferromagnetic long-range ordering below the Néel temperature of about 52 K, with the b axis being the magnetic easy axis. The effective moments have been determined to be 6.18μB and 6.07μB for the pure and the doped crystals, respectively. These values are higher than what is expected on the basis of the spin-only value of 6.70μB with a high-spin d6 configuration for the Fe2+ ion.