Nontraditional intrinsic luminescent (NTIL) polymers are an emerging class of luminescent polymer materials, and the molecular design of novel NTIL polymer luminogens is highly desirable. Here, a series of aggregation-induced emission (AIE) type NTIL polymers, including polytriphenyl­methyl azide, polyfluoro­triphenylmethyl azide, polydifluoro­triphenylmethyl azide, polychloro­triphenylmethyl azide, and polydichloro­triphenylmethyl azide, have been synthesized through reversible addition–fragmentation chain transfer (RAFT) polymerization-induced emission (PIE) successfully. Investigations reveal that the triphenylmethyl azide moiety is a novel PIE luminogen for the molecular design of NTIL polymers, where triphenylmethyl azide is nonemissive but triphenylmethyl azide-containing polymers are emissive. Further applications were performed for explosive detection and luminescence energy transfer applications. Therefore, this work expands the molecular structure library of NTIL and AIE materials that might cause inspirations in different fields including click chemistry, living polymerization, PIE, AIE, and NTIL.