Despite the prosperity of membrane technology, the separation efficiency for Mg 2+ /Li + mixture is still far from satisfactory. Herein, a novel thin-film nanocomposite (TFN) membrane was developed by loading polyhydroxylated fullerene (PHF) via interfacial polymerization. The effects of the PHF dosages on the as-developed membranes were investigated comprehensively by XPS, SEM, AFM, contact angle measurements, as well as nanofiltration tests. The results revealed the TFN membrane containing 0.01% (w/v) PHF exhibited the optimum performances. The membrane showed a pure water flux of 6.7 LÁm −2 Áh −1 Ábar −1 and salt rejections with the order of Na 2 SO 4 (95.6%) > MgSO 4 (93.6%) > MgCl 2 (89.9%) > NaCl (22.6%) > LiCl (16.3%). The membrane not only presented a separation factor of 13.1 in separating Mg 2+ /Li + mixtures, but also demonstrated excellent antifouling ability, which enables membrane regeneration without operation break, suggesting its great potentials in the recovery of Li + from brine or seawater.