The catalyst for direct ethanol synthesis (DES) from syngas was investigated in this work, which is Co/La2O3 doped La4Ga2O9. The catalyst was prepared by using LaCo1-xGaxO3 with perovskite phase as the precursor to intensify the interaction in the elements of Co, La and Ga. The catalysts were characterized by using XRD, H-2-TPR, TEM, EDS, XPS, BET, ICP and TG techniques. This catalyst showed high selectivity to ethanol and excellent stability including excellent resistance to sintering and carbon deposition. It seems that the ethanol is generated in the interface between metallic Co and La4Ga2O9, and in the interface cobalt would be positively charged due to the interaction between Co nanoparticles and La4Ga2O9. The results and the related discussions indicate that Co/La2O3-doped La4Ga2O9 catalyst is a promising catalyst for DES from syngas. Graphical abstracts.