Surface chemical modification allows for the rational construction of biochar with desirable structures and functionalities for environment purification. Fruit-peel-derived adsorbing material has been well studied in the adsorption of heavy-metal removal due to its abundance and non-toxicity, but its precise mechanism in removing chromium-containing pollutants remains unclear. Herein, we explored the potential application of engineered biochar prepared from fruit waste via chemical modification to remove chromium (Cr) from an aqueous solution. By synthesizing two types of agricultural residue-derived adsorbents, including pomegranate peel adsorbent (PG) and its modified product, pomegranate-peel-derived biochar (PG-B), via chemical and thermal decomposition methods, we elucidated the adsorption property of Cr(VI) on the studied materials and identified the cation retention mechanism of the adsorption process. Batch experiments and varied characterizations demonstrated that superior activity was exhibited in PG-B, which can contribute to the porous surfaces caused by pyrolysis and effective active sites resulting from alkalization. The highest Cr(VI) adsorption capacity is obtained at pH 4, a dosage of 6.25 g L−1, and a contact time of 30 min. The maximum adsorption efficiency of 90.50% in a short period (30 min) was obtained on PG-B, while PG reached a removal performance of 78.01% at 60 min. The results from kinetic and isotherm models suggested that monolayer chemisorption dominated the adsorption process. The Langmuir maximum adsorption capacity is 16.23 mg g−1. This study shortened the adsorption equilibrium time of pomegranate-based biosorbents and presents positive significance in designing and optimizing waste fruit-peel-derived adsorption materials for water purification.