Efficient electromagnetic waves absorbing materials while preserving structural integrity based on MIL-53(Fe)/reduced graphene oxide composites remains a challenging task. Most reported preparation techniques compromise structural integrity which limits its practical applications. This study reports innovative method by carefully controlling pyrolysis in a tubular furnace to produce Pyrolyzed MIL-53(Fe)/reduced graphene oxide (P-MIL-53(Fe)/RGO) composites to safeguard structural integrity while preserving RGO’s structure and achieving high EMI shielding efficiency. Various mass ratios of reduced graphene oxide were investigated (15%, 20%, and 30%) to indicate the impact of calcination in changing the degree of graphitization and its effect on the shielding performance. P-MIL-53(Fe)/RGO30 stands out, achieving notable total shielding effectiveness (SET) of 46.5 dB and absorption shielding efficiency (SEA) of 40.3 dB with 2 g of reduced graphene oxide (5 mm thick). The study offers a simple strategy to produce the desired composite with preserved reduced graphene oxide’s structural integrity which has a potential EMI shielding performance. These insights hold promise for diverse applications demanding robust, high-performance electromagnetic wave shielding materials.