In　this　study,　the　occurrence　state　and　distribution　characteristics　of　gallium　(Ga)　in　zinc　refinery　residue　were　investigated　by　dilute　acid　pre-washing　to　enrich　Ga　in　zinc　refinery　residue,　followed　by　silane　coupling　agent　pretreatment　and　epoxy　resin　curing,　and　then　analyzed　using　scanning　electron　microscopy,　focused　ion　beam　micro-slicing　technique　and　transmission　electron　microscopy.　The　acid　washing　increased　the　mass　ratio　of　Ga　from　0.92%　to　2.12%.　Energy-dispersive　spectroscopy　and　select　area　electron　diffraction　revealed　that　Ga　occurred　as　tiny　ring-like　particles　of　gallobeudantite　(a　Pb-jarosite)　that　intimately　envelop　the　previously　formed　K-jarosite　fine-grained　inclusions.　Density　functional　theory　calculations　showed　that　the　interplanar　spacings　of　the　new　phase　formed　after　Ga　substitution　for　Fe　in　Pb-jarosite　(3.413 Å　and　5.505 Å)　were　in　good　agreement　with　the　actual　measured　values,　further　confirming　that　Ga　substitution　for　Fe　in　Pb-jarosite　was　achieved.　The　kinetical　model　explains　the　formation　of　multiple　phases　during　precipitation　in　the　treatment　of　zinc　leaching　solution.　Compared　to　existing　studies,　this　work　reveals　the　spatial　distribution　of　gallium　with　higher　resolution　and　jointly　determines　the　gallium-containing　phases　through　experimental　analysis　and　simulation　calculations.　This　microanalytical　method　enhances　the　understanding　of　Ga　species　formation　during　zinc　refining,　aiding　in　their　distribution　control　and　process　optimization.　Graphical　abstract:　(Figure　presented.)　©　The　Author(s),　under　exclusive　licence　to　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature　2024.