A novel hybrid catalyst system containing alkali formate and Cu/MgO-Na was developed to synthesize methanol from syngas via ethyl formate in a slurry reactor. The results exhibited that high CO conversion (>80%) and methanol selectivity (similar to 90%) with a mass space velocity of 1800 L(STP)/(h kg) were achieved at a low temperature of 433 K and at 5.0 MPa. A synergic function between HCOOM (M = Li, Na, K, Rb and Cs) and Cu/MgO-Na was in existence for promoting the reaction performance, in which sodium formate showed the optimizing synergy with Cu/MgO-Na catalyst. In addition, the nature of the solid copper catalysts also had a remarkable influence on the catalytic activity. (C) 2008 Elsevier B.V. All rights reserved.