The　properties　of　polyethylene　are　highly　dependent　on　the　variety　and　quantity　of　substitutions.　Generally,　polyethylene　can　only　be　fully　substituted　with　fluorine　atoms,　mainly　e. g.,　polytetrafluoroethylene　and　nafion,　because　atomic　radius　of　fluorine　atom　is　small　enough.　The　preparation　of　fully　substituted　polyethylene　analogues　(FSPEA)　and　their　non‐traditional　intrinsic　luminescence　(NTIL)　are　attractive,　especially　for　substitutions　with　relatively　larger　atomic　radii　than　a　fluorine　atom.　Here,　Barbier　polymerization‐induced　emission　(PIE)　is　demonstrated　as　a　universal　method　for　the　molecular　design　of　NTIL　type　FSPEAs　with　intriguing　aggregation‐induced　emission　(AIE)　behaviors.　Through　Barbier　polymerization　of　diphenyldichloromethane　and　different　peroxyesters　in　the　presence　of　Mg　in　one　pot,　a　series　of　FSPEAs,　including　polytriphenylethanol　(PTPE),　polydiphenylfurylethanol　(PDPFE),　polydiphenylthiophenylethanol　(PDPTE)　and　polydiphenylnaphthylethanol　(PDPNE)　have　been　successfully　prepared.　Further　potential　applications　for　explosive　detection,　artificial　light‐harvesting　system　and　white　phosphor‐converted　light‐emitting　diode　are　investigated.　Therefore,　this　work　opens　up　a　new　approach　for　the　molecular　design　of　FSPEA　with　non‐conjugated　luminescence,　which　may　cause　inspirations　to　different　research　fields　like　polyolefin　and　luminescent　materials.