One new benzimidazole derivative copper(II) complex 1(C10H6Cu N2, Mr = 217.71) has been synthesized and characterized by FT-IR and X-ray single-crystal diffraction. It crystallizes in orthorhombic, space group Pbcn with a = 17.417(2), b = 8.9963(8), c = 11.3432(9) ?, V = 1777.3(3) ?3, Z = 8, μ(Mo Kα) = 2.403, F(000) = 872, Dc = 1.627 g/cm3. The final R = 0.0598 for 1153 observed reflections with I 〉 2σ(I) and w R = 0.17 for all data. The in vitro anti-cancer activities of 1, Cu Cl2 and the benzimidazole ligand L were investigated using human cervical(Hela) and hepatocellular carcinoma(Hep-G2) cancer cell lines. The copper(II) complex can greatly inhibit the cell proliferation and show stronger cytotoxic activities against the tested cancer cell lines than both the ligand and copper(II) salt.