Three new Cu(I) CPs, namely, {[Cu₂(DPMF)₃(CN)₂]}_n (1), {[Cu₂(DPMF)₂(CN)₂]·DMSO}_n (2), and {[Cu(DPMF)(CN)]·DMAC·MeOH}_n (3) were synthesized for the first time using an AIE ligand DPMF [DPMF = 4,4′-((9H-fluoren-9-ylidene)methylene)dipyridine]. X-ray structural analysis has revealed that 1 shows a 1D double-chain structure, 2 displays a hexagonal graphene-like 2D layer architecture with 6³-hcb topology and 3 exhibits a 3D framework with 6⁶-dia topology, in which DPMFs are arranged in a windmill-like shape. The differences in their structures are mainly due to the diverse torsions of the DPMF bridges. Furthermore, 3 possesses excellent thermal and solvent stability, and the luminescence measurements indicate that 3 can detect TNP with high sensitivity and selectivity and good recyclability. The emission quenching effect is realized by the energy transfer and electron transfer between 3 and TNP. Moreover, a luminescent test paper is designed to realize the portable detection of TNP in practical applications. These experimental results suggest that 3 can be a potential sensor for TNP.