In this work, a series of catalysts of LaCo1-xGaxO3 with perovskite phase supported on ZrO2 was prepared by combining the citrate complexing method with incipient impregnation. The catalysts of LaCoO3/ZrO2 and Co3O4-Ga2O3/ZrO2 were similarly prepared and used for comparison. The catalysts were characterized by using BET, XRD, H-2-TPD, H-2-TPR, CO-TPD, TG, XPS and TEM techniques. Reducing LaCo(1-x)GaxO(3)/ZrO2 resulted in forming mixed oxides of La-Ga-O modified Co/ZrO2, which was used as the catalyst for higher alcohols synthesis from syngas. The prepared catalyst exhibited very high selectivity to higher alcohols especially to ethanol, high resistance to sintering, high resistance to carbon deposition and good activity, which are attributed to Ga-doping made Co in positive charge, the confinement of mixed oxides of La-Ga-O for Co nanoparticles, the restriction of Ga-doping for carbon formation and the high dispersion of Co nanoparticles, respectively.