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Luminescence porous HPU-12 displays selective quenching detection for Fe3+ and nitrophenolic compound by the interaction between the Fe3+ and N and O atoms in the channels and the overlap of the absorption of nitrophenols with the excitation and emission of HPU-12 , respectively. • Luminescent porous metal-organic framework HPU-12 was prepared. • Two-fold interpenetrated HPU-12 contains 3D pore channels covered with N- and O-coordinated active sites. • HPU-12 was investigated as a luminescent probe for the selective detection of Fe3+ and nitrophenols. • The luminescence quenching mechanism of Fe3+ and nitrophenols on HPU-12 was studied. A porous luminescent MOF {[Zn(L)]·4H 2 O·2CH 3 CN} n (HPU-12) based on a bifunctional ligand, 5-(3,5-Di-pyridin-4-yl- [1,2,4] triazol-1-ylmethyl)-isophthalic acid (H 2 L), has been synthesized. Structural analysis shows that the two-fold interpenetrated HPU-12 contains 3D pore channels covered with N- and O-coordinated active sites. The luminescence investigation demonstrates that the luminescent HPU-12 can realize the selective detection for Fe3+ by quenching the emission of the HPU-12 via the interaction between the Fe3+ and N and O atoms in the pore channels. In addition, the luminescence of the HPU-12 could be selectively and sensitively quenched by nitrophenolic compound because of the overlap of the absorption of the nitrophenolic compound with the excitation and emission of HPU-12. [ABSTRACT FROM AUTHOR]