Stimuli-responsive　luminescent　polymers　play　important　roles　in　polymer　science　and　are　generally　designed　through　polymerization　or　post-polymerization　modification　with　both　stimuli-responsive　and　luminescent　moieties,　which　involves　multistep　synthetic　procedures.　Here,　we　demonstrate　a　one-pot　strategy　for　the　molecular　design　of　stimuli-responsive　luminescent　polymers　through　Barbier　single-atom　polymerization-induced　emission　(PIE).　The　incorporation　of　the　N,N-dimethyl　moiety　into　the　polymer　chain　endows　the　polymers　with　both　stimuli-responsive　and　red-shifted　nonconjugated　emission　properties.　This　nonconjugated　luminescence　is　revealed　with　the　through-space　conjugation　effect　caused　by　polymer　chain　entanglement.　The　prepared　stimuli-responsive　luminescent　polymers　exhibit　intriguing　substitution　position　related　structure-property　relationships,　where　only　para　N,N-dimethyl　substituted　polymers　exhibit　acid/base　responsive　properties.　Further　applications　in　ng　level　explosive　detection　on　test　paper　and　luminescent　encryption　are　carried　out　as　well.　This　work　therefore　opens　a　new　avenue　for　the　molecular　design　of　stimuli-responsive　luminescent　polymers　in　one　pot,　which　expands　the　methodology　and　structure　libraries　of　stimuli-responsive　luminescent　polymers.　©　2022　The　Royal　Society　of　Chemistry.