The present work introduces a new sorbent, so-called PANI/MIL100(Fe), for removing Pb (II) and Cr (VI) from wastewater. The successful preparation of PANI/MIL100(Fe) was verified via Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller (BET) characterizations. This adsorptive material showed a microporous structure with surface area magnitudes of up to 261.29 m2/g, a total pore volume of 0.2124 cm3/g, and a pore size distribution of around 1.2 nm. The maximum adsorption capacities of PANI/MIL100(Fe) for Cr (VI) (pH = 2) and Pb (II) (pH = 6) were obtained as 72.37 and 81.76 mg/g, respectively. The isotherm modeling assessments illustrated that the sorption of Pb (II) and Cr (VI) was consistent with the Sips model (R2 > 0.99), while the adsorption kinetics were suited to a pseudo-second-order model (R2 > 0.95). Thermodynamic studies of both metal ions demonstrated the spontaneous and endothermic nature of the process. The reusability of the PANI/MIL100(Fe) indicated promising adsorption properties for Pb (II) and Cr (VI) up to three cycles. Moreover, the XRD and FT-IR spectroscopy results after adsorption/desorption showed excellent stability of the adsorbent and physisorption mechanism, wherein electrons were exchanged between the PANI/MIL-100(Fe) and Pb (II) and Cr (VI). Finally, the findings suggested that PANI/MIL100(Fe) can be considered an efficient and environmentally friendly adsorbent to remove Pb (II) and Cr (VI) from wastewater.