The　development　of　catalysts　for　the　direct　one-step　conversion　of　syngas　to　higher　alcohols　is　still　a　challenge.　In　this　study,　different　alkali　metal-modified　MCoMo/Al2O3　(M = Li,　Na,　K,　and　Cs)　catalysts　were　prepared　by　impregnation　and　temperature-programmed　carbonization　process.　Characterization　by　XRD,　H2-TPR,　and　XPS　revealed　that　the　introduction　of　alkali　metals　increases　the　crystallinity　of　Mo2C,　decreases　the　reducibility　of　the　catalyst,　as　well　as　increases　the　surface　high-valent　Mo　content.　The　catalysts　were　evaluated　for　activity　at　300 °C,　3.0 MPa,　18,000　mL·gMo−1·h−1,　H2/CO = 2.　The　evaluation　results　found　that　with　the　increase　in　the　electron-giving　capacity　of　alkali　metals,　the　CO　conversion　rate　gradually　decreased　from　98.8%　to　46.3%.　While　the　alcohol　selectivity　showed　the　opposite　trend,　increasing　from　14.4%　to　54.9%.　Notably,　the　addition　of　K　and　Cs　significantly　increased　the　alcohol　selectivity　in　the　catalyst　product,　from　8.3%　to　50.5%　and　54.9%,　respectively.　Moreover,　the　ratio　of　higher　alcohols　in　the　alcohol　product　increased　significantly　from　10.5%　to　nearly　80%.　Finally,　in　situ　DRIFT　characterization　of　the　catalysts　with　different　alkali　metal　modifications　was　carried　out　to　investigate　the　changes　in　the　reaction　process　intermediates　and　to　summarize　the　possible　reaction　routes.　©　2025　Wiley-VCH　GmbH.