A porous luminescent zinc(II) metal-organic framework (MOP) with a NbO net [Zn-2(tptc)(apy)(2-x)(H2O)(x)]center dot H2O (1) (where x approximate to 1, apy = aminopyridine, H(4)tptc = terpheny1-3,3 '',5,5 ''-tetracarboxylic acid), constructed using paddlewheel [Zn-2(COO)(4)] clusters and pi-electron-rich terphenyl-tetracarboxylic acid, has been solvothermally synthesized and characterized. Interestingly, the material displays efficient, reversible adsorption of radioactive I-2 in vapor and in solution (up to 216 wt %). The strong affinity for I-2 is mainly due to it having large porosity, a conjugated pi-electron aromatic system, halogen bonds, and electron-donating aminos. Furthermore, luminescent study indicated that 1 exhibits high sensitivity to electron-deficient nitrobenzene explosives via fluorescence quenching.