Two 3D Zn(II) and Pb(II) isophthalates, [Zn(ip)](n) (1) and [Pb-4(mu(4)-O)(ip)(3)(H2O)](n) (2) (H(2)iP = isophthalic acid), have been prepared under hydro(solvo)thermal conditions and characterized by single-crystal X-ray diffraction. The two complexes crystallize in different space groups (P4(3)2(1)2 for 1 and P2(1)/c for 2) and have different bridging modes of the ip ligand. The 3D framework of 1 is constructed by the interconnection of ZnO4 polyhedra via ip ligands, which represents a chiral net with PtS-type topology. In contrast, complex 2 is formed by the combination of Pb4O-cluster secondary building units and has a novel (3.4.5)(3(2).4(5).5(6).6(7).7(2)) topology, which is the first ever example of a (3,7)-connected net. Complex 1 displays a second harmonic generation efficiency of about 1.5 times that of KH2PO4. Optical properties and thermal stabilities of the two complexes have been studied. Additionally, the calculations of band structure and density of states of 1 have also been performed with the density functional theory method.