Two　types　of　amorphous　ZrO2　(am-ZrO2)　catalysts　were　prepared　by　different　co-precipitation/reflux　digestion　methods　(with　ethylenediamine　and　ammonia　as　the　precipitant　respectively).　Then,　copper　and　potassium　were　introduced　for　modifying　ZrO2　via　an　impregnation　method　to　enhance　the　catalytic　performance.　The　obtained　catalysts　were　further　characterized　by　means　of　Brunauer-Emmett-Teller　surface　areas　(BET),　X-ray　diffraction　(XRD),　H2-temperature-programmed　reduction　(H2-TPR),　and　In　situ　diffuse　reflectance　infrared　spectroscopy　(in　situ　DRIFTS).　CO　hydrogenation　experiments　were　performed　in　a　fixed-bed　reactor　for　isobutanol　synthesis.　Great　differences　were　observed　on　the　distribution　of　alcohols　over　the　two　types　of　ZrO2　catalysts,　which　were　promoted　with　the　same　content　of　Cu　and　K.　The　selectivity　of　isobutanol　on　K-CuZrO2　(ammonia　as　precipitant,　A-KCZ)　was　three　times　higher　than　that　on　K-CuZrO2　(ethylenediamine　as　precipitant,　E-KCZ).　The　characterization　results　indicated　that　the　A-KCZ　catalyst　supplied　more　active　hydroxyls　(isolated　hydroxyls)　for　anchoring　and　dispersing　Cu.　More　importantly,　it　was　found　that　bicarbonate　species　were　formed,　which　were　ascribed　as　important　C1　species　for　isobutanol　formation　on　the　A-KCZ　catalyst　surface.　These　C1　intermediates　had　relatively　stronger　adsorption　strength　than　those　adsorbed　on　the　E-KCZ　catalyst,　indicating　that　the　bicarbonate　species　on　the　A-KCZ　catalyst　had　a　longer　residence　time　for　further　carbon　chain　growth.　Therefore,　the　selectivity　of　isobutanol　was　greatly　enhanced.　These　findings　would　extend　the　horizontal　of　direct　alcohols　synthesis　from　syngas.　©　2019　by　the　authors.　Licensee　MDPI,　Basel,　Switzerland.