A porous luminescent zinc(II) metal–organic framework (MOF) with a NbO net [Zn2(tptc)(apy)2–x(H2O)x]·H2O (1) (where x≈ 1, apy = aminopyridine, H4tptc = terphenyl-3,3″,5,5″-tetracarboxylic acid), constructed using paddlewheel [Zn2(COO)4] clusters and π-electron-rich terphenyl-tetracarboxylic acid, has been solvothermally synthesized and characterized. Interestingly, the material displays efficient, reversible adsorption of radioactive I2in vapor and in solution (up to 216 wt %). The strong affinity for I2is mainly due to it having large porosity, a conjugated π-electron aromatic system, halogen bonds, and electron-donating aminos. Furthermore, luminescent study indicated that 1exhibits high sensitivity to electron-deficient nitrobenzene explosives via fluorescence quenching.