The hydrofluoric acid-resisting aluminum compounds (AlF3, AlPO4, AlN) supported with Ni catalyst were prepared by the wetness impregnation and tested for dehydrofluorination of hydrofluoroalkane to synthesize fluoroolefins. It is found that Ni/AlF3 catalyst has the best catalytic performance, CF3CFH2 conversion of 29.3% after the reaction at 430 °C for 30 h, CF2HCH3 conversion of 31.8% after the reaction at 250 °C for 30 h, respectively. Comparatively, dehydrofluorination temperature of CF3CFH2 is higher than CF2HCH3 over the aluminum compounds catalyst, and the activity of catalysts is related with Lewis acidity. For the aluminum compounds catalyst, addition of Ni had promoted the activity and stability of Lewis acidic catalysts, it is attributed to synergistic catalysis of Lewis acid sites and Ni.