Activated carbon-supported Mo-Co-K sulfide catalysts, prepared by stepwise impregnation, were used in the synthesis of higher alcohols via CO2 hydrogenation. The catalysts with varying Mo contents and defined K/Mo and Co/Mo molar ratios exhibited relatively high CO2 conversions and high selectivity to total alcohols and C2+ alcohols. Moreover, the influence of calcination conditions on the sulfidation states and catalytic performance was studied. The surface sulfur runoff of the supported catalysts can be effectively suppressed by online calcination. As a result, the selectivity to total alcohols and C2+ alcohols can be improved.