The　aspect　ratio　modulation　in　the　alcoholysis　process　is　highly　significant　for　the　production　of　high-quality　sucralose.　In　this　work,　antisolvent　crystallization　(ASC)　accompanied　by　preferred　orientation　was　first　adopted　in　the　sucralose　separation,　based　on　which　simultaneous　modulations　on　aspect　ratio,　solubility,　and　stability　have　been　realized.　In　detail,　after　the　alcoholysis　process　in　methanol,　four　antisolvents　bearing　different　functional　groups　were　used　in　ASC,　i.e.,　isopentanol　(IPN),　isovaleraldehyde　(IVD),　isovaleric　acid　(IVA),　and　isobutyl　propionate　(IBP).　To　our　interest,　when　IVA　was　used　as　the　antisolvent,　the　highest　separation　efficiency　(49.33%),　fastest　crystallizing　rate　(5.64%/h),　lowest　aspect　ratio　(1.55),　and　solubility　(9.28　wt　%)　and　good　thermal　stability　(131.65　°C)　of　sucralose　were　achieved.　Single　crystal　structures　of　sucralose　using　different　antisolvents　have　been　determined.　Sucralose　using　IVA　as　the　antisolvent　exhibits　the　greatest　molecular　distortion　and　strongest　intermolecular　C-H···Cl　hydrogen　bonds;　thus,　the　preferred　growth　along　{002}/{011}　directions　has　occurred　and　accounted　for　its　lower　aspect　ratio,　worse　solubility,　and　better　stability.　The　strongest　methanol···IVA　interactions　due　to　the　presence　of　a　carboxyl　group　can　accelerate　the　formation　of　the　emulsion,　resulting　in　the　fastest　crystallizing　rate.　The　antisolvent　screening　and　the　discovery　about　relative　mechanisms　will　provide　a　theoretical　guide　for　the　production　of　high-quality　sucralose.　©　2023　The　Authors.　Published　by　American　Chemical　Society.