In this work, Rh-Co/La2O3-SiO2 showed excellent selectivity to ethanol for direct ethanol synthesis from syngas. The best catalyst exhibited 42.8% selectivity to ethanol with CO conversion of 12.3% and in 145 h' running maintained stable at 553 K, 3 MPa and GHSV of 3900 mL (g(cat) h)(-1). The investigate results indicated that the interaction of cobalt denoting electron to rhodium adjusted the amounts of carbon monoxide adsorbed associatively and dissociatively, and maybe created a new active site pair of Rh-0/Co delta+ for generating ethanol. Moreover, the mutually doping effect could dilute Co and Rh atoms in Rh-Co nanoparticles (NPs), which effectively suppressed the formation of C2+H and C3+OH, and thus led to the high ethanol selectivity and good anticoking property assisting with the carbon eliminating effect of La2O3. Owing to the high dispersion of Rh-Co NPs, the catalyst showed good activity and high resistance to sintering.