Abstract: A binuclear tin complex [Sn_2Cl_6(μ-OH)_2(DMF)_2]·4DMF has been synthesized through direct reaction of SnCl_4·5H_2O with DMF. Its molecular and crystal structure has been determined by single X-ray diffraction technique. The crystal is triclinic with space group P1. The unit cell parameters are a=0.9153(2), b=1.0722(3), c=1.2192(3) nm, α=63.07(2), β=93.26(2), γ=65.75 (2), V=0.92821(36) nm, D_c=1.649 g·cm~(-3), Z=1, The tin atom in the complex takes six-coordinated distorted octahedral configuration with sp~3 d~2 hybrid. The two tin atoms are connected through hydroxyl bridge to form a plane at the molecular center. The four noncoordinated DMF molecules distribute symmetrically around the dimer. The whole complex has an inversion center which coincides with the gravity center of the parallelogram.