A 2-dimensional Pb(II) metal–organic framework, [Pb(bdc)_0.5(py-Phen)NO₃]_n (SM-3), was synthesized under solvothermal conditions using a mixed ligand approach. SM-3 was assembled using dinuclear SBUs [Pb₂(COO)₂]²⁻, an oxygen donor H₂bdc = 1,4-benzene dicarboxylic acid, and nitrogen donor py-Phen = pyrazino[2,3-f][1,10]-phenanthroline linkers. SM-3 was characterized by elemental analysis, FT-IR, powder-X-ray diffraction, thermal gravimetric analysis, SEM, EDS, TEM, and single-crystal X-ray diffraction techniques. Crystallographic studies confirmed that SM-3 displays a 2D layered structure with unique anagostic (Pb⋯H) interactions. Interestingly, the presence of abundant π-electron-rich rings embellished with free –N donor sites in the framework makes SM-3 an excellent adsorbent that exhibits adsorption performance for iodine and dyes. The experimental results show that SM-3 reversibly adsorbs radioactive iodine in the solution and vapor phases and exhibits selective adsorption performance for hazardous cationic dyes, namely, methylene blue (MB) and rhodamine-B (Rh-B), from aqueous solution. Moreover, the possible mechanism of iodine and dye adsorption was also discussed in detail. Thus, this work is remarkable for coordination chemists to engineer layered MOFs for adsorption purposes and expands their potential characteristics by converting them into 2D MOF nanosheets to further enhance the adsorption of hazardous pollutants for environment protection.