Biochar-based fertilizers show promise in enhancing nutrient utilization and soil health, but their slow-release performance remains a challenge. Herein, hydrogel membranes incorporating iron oxide nanoparticles within a polyvinyl alcohol and starch matrix (Fe/PVA/ST) were synthesized. These membranes were utilized to coat compound fertilizer particles, with biochar powder applied to the outer layer to form what is known as Fe/PVA/ST-BSRFs. The results revealed that Fe/PVA/ST-BSRFs exhibit markedly improved slow-release performance compared to both PVA/ST-BSRFs lacking iron nanoparticles and commercial compound fertilizers. Within a 30-day period, the cumulative leaching ratios of N, P, and K from Fe/PVA/ST-BSRFs with 0.75 % iron content were significantly lower compared to other tested fertilizers, with values of 22.87 %, 34.93 %, and 84.08 %, respectively. Furthermore, the incorporation of iron oxide nanoparticles into the PVA/ST membrane enhanced its swelling and water-retention properties without compromising its biodegradability. Mechanistic investigations revealed that the exceptional slow-release properties of Fe/PVA/ST-BSRFs stem from a combination of nutrient diffusion control outside the membrane and the loose control mechanism of the membrane. Pot tests demonstrated that Fe/PVA/ST-BSRFs effectively promoted the growth of chili plants while ensuring high utilization of N-P-K and improving the nutritional indices of chili fruits. Economic analysis further underscored the promising application prospects of Fe/PVA/ST-BSRFs.