Germanium　is　one　of　the　strategic　scattering　metals,　and　recovering　a　minor　concentration　of　scattering　metals　from　zinc　concentrate＇s　leaching　solution　is　an　essential　resource　worldwide.　Practically,　neutralizing　precipitation　and　the　subsequent　dissolution　are　implemented　to　enrich　scattering　metals　from　zinc　leaching　solution,　facilitating　further　extraction　of　Ge　and　others.　Silicon　poses　significant　challenges　to　the　efficient　extraction　of　Ge　due　to　their　similar　chemical　property　and　the　inert　nature　of　silica.　However,　the　evolution　of　the　Ge　occurrence　state,　especially　its　relationship　with　Si,　during　the　precipitation　and　dissolution　process　in　zinc　hydrometallurgy　is　unclear,　and　there　is　a　lack　of　an　effective　method　to　separate　Si/Ge.　This　paper　started　with　a　detailed　characterization　and　leaching　behavior　of　Ge-enriched　residue　obtained　from　the　plant,　followed　by　a　systematic　investigation　of　Ge　behavior　in　synthetic　Si/Ge　binary　and　Fe/Si/Ge　ternary　systems.　Eventually,　options　for　Ge　enrichment　from　zinc　leaching　solution　and　Si/Ge　separation　are　recommended,　providing　a　practical　framework　for　mitigating　the　negative　influence　of　Si　on　the　extraction　of　Ge　in　zinc　hydrometallurgy.　The　significant　findings　are　that　Ge/Si　are　both　presumably　co-adsorbed　by　Fe(OH)3　colloids　upon　neutralization　to　pH　5　of　zinc　leaching　solution,　which　could　be　acid　redissolved　at　the　unrealistically　high　liquid-to-solid　ratio　of　200/1　at　the　practically　meaningful　liquid-to-solid　ratio　of　5/1,　Si　concentration　is　high　enough　to　quickly　condense　and　polymerize,　resulting　the　formation　of　silica　precipitate　and　permanent　encapsulating　of　Ge　into　silica;　interestingly,　the　Si-O-Ge　bonding　becomes　weakened　with　pH　increasing　up　to　alkaline　region　and　Ge　leaching　rate　exceeding　80%　at　pH　10,　effectively　separating　Ge　from　SiO2.　©　2025　Elsevier　B.V.