Fatty　acid　ethyl　esters　(FAEE)　are　key　target　for　wine　industry　to　diversify　its　production　towards　fruity　flavor.　The　microbial　community　and　functional　enzymes　governing　FAEE　formation　during　Chinese　rice　wine　(Huangjiu)　brewing　were　investigated　in　current　study.　Physicochemical　characteristics　and　FAEE　displayed　distinct　phased　changes,　which　fluctuated　sharply　in　initial　fermentation　and　then　leveling　off　gently.　Except　for　reducing　sugar,　other　factors　and　FAEE　showed　strong　positive　correlations　with　the　dominant　microorganisms.　Based　on　metagenomic　analysis,　Saccharomyces　cerevisiae　and　lactic　acid　bacteria　(LAB)　were　dominant　in　production　of　oxidoreductase,　transferase,　and　isomerase,　which　significantly　contributing　to　FAEE　synthesis.　Besides,　phosphoglycerate　mutase,　pyruvate　decarboxylase,　fatty-acyl-CoA　synthase,　and　trans-2-enoyl-CoA　were　crucial　enzymes　for　the　synthesis　of　FAEE　precursors,　with　S.　cerevisiae　making　substantial　contributions.　Microbe-mediated　metabolic　pathways　elucidated　that　FAEE　was　mainly　synthesized　via　ethanol　and　fatty　acyl-CoA　(C　≤　16)　under　lipase　and　alcohol　acyltransferase　through　S.　cerevisiae　during　Huangjiu　brewing.　The　most　abundant　LAB　mainly　influenced　FAEE　via　pyruvate　metabolism　and　esterase　synthesis.　Co-occurrence　analysis　highlighted　the　importance　of　amino　acids　for　FAEE　formation,　especially　lysine.　The　findings　provide　insights　into　optimizing　FAEE　production　for　enhanced　flavor　quality　of　alcoholic　beverages.　©　2024　The　Authors