This　study　aims　to　achieve　further　progress　in　application　performance　of　polymers　in　cementbased　materials.　The　objective　is　to　establish　the　research　direction　of　superplasticizers　with　ordered　micro-sequence　via　the　innovation　of　synthesis　technology　and　to　clarify　the　correlation　between　the　specific　motifs　in　the　microstructures　of　superplasticizers　and　the　properties　of　cement　pastes.　In　this　study,　a　novel　comb-like　polycarboxylate　superplasticizer　(PCE)　was　synthesized　using　isobutenyl　polyethylene　glycol　(IPEG)　and　hydroxyethyl　acrylate　(HEA)　by　atom　transfer　radical　polymerization　(ATRP)　(defined　as　A-CPCE).　Comb-like　PCE　with　the　same　molecular　weight　as　A-CPCE　was　also　produced　via　conventional　free　radical　polymerization　(defined　as　CPCE).　The　molecular　properties　of　both　polymers　and　the　structural　motifs　of　monomers　therein　were　characterized　via　size　exclusion　chromatography　(SEC),　H-1　nuclear　magnetic　resonance　(H-1　NMR),　C-13　nuclear　magnetic　resonance　(C-13　NMR)　and　MATLAB,　and　furthermore　the　adsorption　behavior　of　PCE　polymers　on　cement　particles　was　analyzed.　Together　with　the　rheological　and　mechanical　properties　of　cement-based　materials,　the　relationship　between　micro-sequence　distribution　and　macro-performance　of　PCEs　was　investigated.　The　results　showed　that　the　monomer　sequence　distribution　in　A-CPCE　was　AAE　and　AAA,　and　the　probability　of　the　acid-ether　ratio　of　4:1　was　16.54%,　meaning　that　relatively　uniform　polymer　species　were　obtained.　The　A-CPCE　molecules　exhibited　the　smaller　hydrodynamic　radius　(R-h=11.7　nm)　and　stronger　adsorption　capacity　(maximum　was　2.3618　mg　center　dot　g(-1))　in　cement　pastes,　which　was　in　good　accordance　with　Langmuir　isotherm　model　and　pseudo-second　order　kinetic　model.　The　dispersing　power　of　PCEs　correlated　with　the　specific　motifs　in　the　microstructures,　thus　indicating　that　A-CPCE　enhanced　the　rheological　performances　of　cement　paste　and　concrete.　In　addition,　the　compressive　strengths　of　concrete　containing　A-CPCE　after　3　d,　7　d　and　28　d　were　16.00　MPa,　28.30　MPa　and　52.9　MPa,　respectively,　which　were　significantly　higher　than　those　of　concrete　with　CPCE.