In order to improve the gas sensitivity of SnO2, Ni-doped and Co-doped nano-powders were prepared by the homogenous co-precipitation method using analytical pure SnCl4•5H2O and NH3•H2O as main materials under different doped ratios n (M2+)/n (Sn4+). The gas sensors were made by the thick film technique on mica substrates. The structure and crystal properties of the samples were investigated by X-ray diffraction (XRD). The results indicated that Sn4+ in the crystal lattice of SnO2 was partly replaced by M2+, which resulted in the change of the M-O bond lengths and the lattice parameters. The sensitivities of the sensors in H2 atmosphere with different concentrations at 75°C were tested. As a result, doped M2+ especially Ni2+ improves its H2 sensitivity, the sensitivities increases linearly with the increasing H2 concentration, and the best doping n(M2+)/n(Sn4+) of preparing gas-sensing material were obtained. The results show that doping which leads to the asymmetry of electrovalent balance of M-O octahedrons improves the activities and semiconductor properties of the powders. These studies play an important part in detecting reductive gases in special environment.