Two complexes, namely [Zn(bpeb)(sda)] (1) and [Zn(poly-bpeb)(sda)] (2), were synthesized by an organic ligand with an extensively conjugated system, bpeb = 1,4-bis[2-(3-pyridyl) vinyl]-benzene, H2sda = sulfonyldibenzoic acid and d10 metal centers Zn2+. Structural analysis revealed that compound 1 was nonporous and possessed 7-fold interpenetrated three-dimensional (3D) frameworks constructed from one-dimensional (1D) Zn-bpeb and Zn-sda chains. Interestingly, due to the short distance between the vinyl groups from two neighboring bpeb ligands, compound 1 could undergo a photochemical [2 + 2] polymerization reaction to generate 2 in a single-crystal to single-crystal (SCSC) manner under the irritation of UV. Moreover, the organic polymer in 2 could be depolymerized by heating to realize the reversible transformation from 2 to 1. Furthermore, both compounds 1 and 2 could be used as fluorescent sensors for 2,4,6-trinitrophenol (TNP) with high selectivity and sensitivity.