The role of Cu:Co composition in bi-metallic Cu-Co/ZnAl 2 O 4 catalysts on higher alcohol synthesis (HAS) was investigated at H 2 :CO = 4. The addition of Cu strongly facilitated Co reduction upon catalyst activation and suppressed coke deposition during HAS. Formation of predominantly hydrocarbons and higher alcohols was observed on the bi-metallic catalysts. Co/ZnAl 2 O 4 produced mainly CH 4 and Cu/ZnAl 2 O 4 mainly CH 3 OH, while at Cu:Co = 0.6 the best ethanol selectivity of 4.5 % was reached. The microstructure of the spent catalysts confirmed a close interaction of Cu and Co.