As　a　new　generation　of　safe　sweeteners,　sucralose　(TGS)　has　been　extensively　used　in　food　and　beverages.　However,　the　comprehensive　identification　and　quantification　of　chlorination　products　have　never　been　conducted,　which　renders　the　difficulty　in　mechanism　study　and　hinders　further　technology　upgrading.　Herein,　by　using　preparative　liquid　chromatography　(PLC),　comprehensive　separation　and　purification　have　been　executed　on　complicated　chlorination　products　after　undergoing　acylation/chlorination　reactions.　Consequently,　29　chlorinated　products　classified　into　eight　kinds　of　positional　isomers　(purity　＞　97　%　wt)　have　been　prepared　for　the　first　time.　They　were　further　structurally　determined　by　1D/2D　nuclear　magnetic　resonance　(NMR)　and　high-resolution　mass　spectrum　(HR-MS).　Furthermore,　a　fast/convenient　analysis　method　on　chlorinated　products　using　high-performance　liquid　chromatography　with　evaporative　light　scattering　detection　(HPLC-ELSD)　has　been　established,　in　which　main-product　4,1　＇,6　＇-trichlorosucrose-6-acetate　(TSA-6)　and　other　by-products　could　be　quantified　simultaneously.　Upon　optimization　on　the　HPLC　conditions,　the　standard　curves　of　29　compounds　exhibit　good　linear　degree　(R-2　＞　0.9992)　and　excellent　spiked　recoveries　(97.8　%similar　to　102.4　%),　hinting　at　its　high　accuracy,　sensitivity　(detection　limit:　0.5　similar　to　2.0　mu　g/mL),　repeatability　(intra-day　and　the　inter-day　deviations　RSD　＜　3.10　%,　n　=　6).　It　can　detect　38　chlorination　by-products　in　42　min　with　excellent　separation　efficiency　(Rs　＞　1.5).　Finally,　based　on　the　structural　determination　of　28　by-products,　the　generation　pathways　of　TSA-6　and　by-products　were　proposed:　the　multi-step　chlorination　on　sucrose-6-acetate　(SA-6),　gradient　carbonization,　and　polymerization.　The　proposal　of　the　quantification　method　and　the　determination　of　by-products　can　be　beneficial　for　high-quality　TGS　production.