One of the hottest research topics over the last decades was the valorization or/and recycling of agro-industrial wastes into different valuable liquid or solid products, which is considered a sustainable and low-cost approach. In this study, we developed zero-valent iron nanoparticles from Palm Petiole Extract (P-NZVI) using a green and straightforward approach. The as-synthesized P-NZVI was used to adsorb Cr(VI) in water. The physico-chemical characterizations of P-NZVI, including the particle size, crystalline structure, surface area, morphology, and functional groups, were investigated via several techniques such as UV-vis spectroscopy, SEM, TEM, XRD, FTIR, AFM, DLS, pHZPC measurement, and BET analysis. The adsorption performance of P-NZVI was studied under different operational parameters, including pollutant concentration, pH, temperature, and adsorbent mass. The adsorption rate was found to be 89.3% within 40 min, corresponding to the adsorption capacity of 44.47 mg/g under the following conditions: initial Cr(VI) concentration of 40 mg/L, pH 5, and a P-NZVI dosage of 1 g/L. It was found that the adsorption pattern follows the Langmuir and the pseudo-second-order kinetic models, indicating a combination of monolayer adsorption and chemisorption mechanisms. The thermodynamic study shows that the adsorption process is endothermic and spontaneous. The reusability of P-NZVI was carried out four times, showing a slight decrease from 89.3 to 87%. These findings highlight that P-NZVI’s could be an effective green adsorbent for removing Cr(VI) or other types of toxic pollutants from water.