To address the technical bottleneck that conventional metal fuels struggle to balance high energy and efficient energy release， the microstructure and composition， combustion process， and energy performance of AlTiV alloy powders are investigated using scanning electron microscopy/energy dispersive spectroscopy （SEM/EDS）， X-ray diffraction （XRD）， flat-flame burner， oxygen bomb calorimeter， and thermogravimetry-differential thermal analysis （TG-DSC）. The detonation heat performance of their hydroxyl-terminated polybutadiene （HTPB） propellants is further verified via the adiabatic method. The results show that AlTiV alloy powders have a high-sphericity body-centered cubic （BCC） solid solution structure， and their combustion process consists of four distinct stages： ignition， self-sustained combustion， micro-explosion， and dispersed combustion. Increasing Ti content shortens both the ignition delay and micro-explosion time and enhances the intensity of micro-explosion， while vanadium oxides can damage the surface oxide layer and promote the gas-phase combustion of aluminum vapor. The Al₃₀Ti₂₅V₄₅ （ATV30） alloy powder exhibits the optimal comprehensive performance， with a combustion efficiency of 97.35% and a volumetric calorific value of 86590 J·cm^-3. It initiates rapid oxidation at 600 ℃， and its oxidation efficiency reaches 97.62%， which is highly consistent with its combustion efficiency. When ATV30 is used to replace 25% of aluminum powder in HTPB propellants， the volumetric explosive heat of the propellant is increased by 2.3%. It is confirmed that AlTiV alloy powders can improve the explosive heat performance of propellants through the synergistic effect of micro-explosion and gas-phase combustion， which provides a theoretical basis and experimental support for the application of novel metal fuels in solid propellants.