Ludwigite ore, as a representative complex-associated mineral, suffers from extremely low resource utilization efficiency due to its lean composition, fine dissemination, and heterogeneous nature. Leveraging the compositional constituents of ludwigite ore, this study pioneers the development of a ludwigite ore–polyimide resin composite for medical X-ray shielding applications. Systematic investigations were conducted on the effects of the addition amount of ludwigite, tube voltage, and tube current on shielding performance. The study revealed that with the increase of the addition amount of ludwigite ore, the composite material exhibited enhanced X-ray shielding effectiveness. However, as the radiation intensity (tube voltage and current) increased, the shielding performance gradually diminished, indicating a high sensitivity of the shielding effectiveness of the ludwigite ore addition amount to tube voltage variations. Notably, a 3 cm-thick shielding composite achieved a peak shielding efficiency of 88.28%, with a linear attenuation coefficient of 0.7146 cm⁻¹ and a half-value layer thickness of 0.97 cm. This research not only opens up a new pathway for the high-value utilization of Ludwigite resources but also provides a cost-effective composite solution for medical X-ray radiation protection applications.