Direct　production　of　higher　alcohols　remains　a　great　challenge　in　syngas　conversion　process.　Herein,　MMo2C/Al2O3　and　KMMo2C/Al2O3　catalysts　promoted　by　different　transition　metals　M　(M=Co,　Fe,　Cu,　Ni,　Zn,　Nb)　and　alkali　metal　(K)　were　prepared　by　impregnation　method　to　investigate　the　effect　on　CO　hydrogenation　to　higher　alcohols　under　milder　reaction　conditions　(300°C,　3.0　MPa).　The　catalysts　were　characterized　with　XRD,　H2-TPR,　and　XPS.　It　was　found　that　the　addition　of　transition　metals　and　K　resulted　in　the　decrease　of　low-valent　Mo　species　on　the　catalyst　surface,　which　facilitated　the　generation　of　Mo4+　during　the　reaction.　Increase　in　Mo4+　content　facilitates　the　conversion　of　CO　to　CO*,　which　provides　more　CO　insertion　sites　for　the　generation　of　alcohols.　Moreover,　the　introduction　of　K　also　enhances　the　interaction　of　transition　metals　with　Mo,　which　accelerates　the　formation　of　alcohols　in　the　reaction.　Meanwhile,　the　transition　metal　and　Mo2C　work　together　to　promote　the　dissociative　adsorption　of　CO.　The　production　of　higher　alcohols　is　facilitated　by　the　synergistic　effect　of　the　two　mentioned　above.　Overall,　the　KCoMo/Al2O3　and　KFeMo/Al2O3　catalysts　exhibited　high　selectivity　for　higher　alcohols,　reaching　73.9　%　and　71.3　%　for　C2+OH　in　the　alcohol　products,　respectively.　CO　conversion　of　KFeMo/Al2O3　catalyst　can　reach　84.9　%　with　excellent　stability　in　the　reaction.　Moreover,　the　possible　pathways　of　the　reaction　were　obtained　by　in-situ　DRIFT　characterization.　©　2024　Elsevier　Ltd