For the first time a systematic research on the catalytic activity of CuXn (X=Cl, Br, I; x=1,2) for the cross-coupling reaction of alkyl halides with Grignard reagents was carried out and environmentally friendly, economical CuBr2 showed highest catalytic activity among the catalyst. The conditions of the cross-coupling reaction were studied. The suitable amount of catalyst, reaction temperature and time are 0.3% mol (based on alkyl halide), 67°C (reflux), 6 h, respectively. Under the optimal conditions, the yields of the cross-coupling could reach up to 93%. Moreover, Grignard reagent with an electron-rich group reacted rapidly and with an electron-withdrawing group reacted sluggishly.