In this work, a new stable monometallic Pb-based metal− organic framework (MOF) [PbL] n (1) was obtained by a designed N,Ocontaining ligand 5-(1H-tetrazol-5-yl)isophthalic acid (H 2 L) for the first time. On the basis of the hard and soft acids and bases (HSAB) principle and the multicoordination modes of L 2− and Pb(II) ions, four new heterometallic MOFs (HMOFs), namely, { 4), and Mn (5)), have been further synthesized by introducing the second metals into the synthesis process of 1, respectively. Complex 1 shows a 3D compact packing structure, while HMOFs 2−5 show the homogeneous 3D porous reticular structures embedding 1D channels with multiple active sites (the unsaturated metal sites and uncoordinated N sites) viewed along the b direction. The resultant HMOFs possess high hydrolytic and thermal stability, owing to the abundant π•••π interactions for the neighboring phenyl rings in the L 2− ligands. Of great importance, it is found that the enhanced luminescence intensities of HMOFs 2 and 3 and the catalytic performances of HMOFs 4 and 5 are demonstrated in comparison with 1. HMOFs 2 and 3 are successfully explored as the nitrobenzene sensors with lower detection limits, and HMOFs 4 and 5 are the outstanding catalysts for the CO 2 cycloaddition. This work may provide some valuable references for the performance variations of one specific monometallic MOF to HMOF materials by introducing the closed/open-shell electron configuration of the second metal ions.