Metal-metal energetic structural materials （ESMs） possess unique thermal reaction characteristics combined with mechanical strength， making them promising candidates for reactive fragment applications. Among them， Al-based ESMs have been extensively investigated due to their high energy-release potential. However， achieving a balance among strength， plasticity， and impact-induced energy release remains challenging， which limits their further development. In this study， Al/Zr/Bi₂O₃ ESMs with an Al/Zr molar ratio of 1.3∶1 and varying Bi₂O₃ contents were fabricated using a ball milling-spin forging process. Structural characterization， thermal analysis， quasi-static compression tests， and ballistic penetration experiments were systematically conducted. The results demonstrate that introducing an appropriate amount of Bi₂O₃ significantly enhances impact-induced chemical energy release while maintaining sufficient load-bearing capacity. Specifically， with Bi₂O₃ additions of 3% and 5%， the energy release at an impact velocity of 0.8 km·s^-1 reached 6.26 kJ·g^-1 and 7.07 kJ·g^-1， respectively， which are approximately 2.8-3.15 times higher than that of the oxidant-free Al/Zr system （2.24 kJ·g^-1）. The velocity threshold for triggering a pronounced chemical reaction in this system was approximately 0.357 km·s^-1. However， when the Bi₂O₃ content reached or exceeded 7%， severe oxidant agglomeration induced interfacial defects and material embrittlement， leading to premature fracture during impact and consequently suppressing the chemical reaction. Furthermore， the mechanisms by which Bi₂O₃ promotes Al/Zr interfacial reactions and enhances energy release were systematically analyzed. This work provides both experimental evidence and theoretical insight for the development of high-efficiency energetic structural materials through optimized oxidant content.