The management of arsenic residue (AR) poses a significant environmental challenge globally. Conventional methods such as landfill, adsorption, and purification often fail to prevent arsenic migration, leading to uncertainties about the final disposition of AR and risks of secondary pollution. Vitrification offers a more stable approach for solidifying AR. This study explores the vitrification mechanism of AR using basalt and evaluates the performance of the resulting fibers. Our findings indicate that increasing the arsenic concentration decreases the high-temperature viscosity of basalt, making fiber drawing more energy-efficient. Incorporating a small amount of arsenic (approximately 0.4 mol%) significantly enhances the tensile strength of basalt fibers (BFs) by 10 %, attributed to reduced viscosity and improved fiber formation with fewer internal defects. Additionally, the flexural strength and stiffness modulus of asphalt mixtures are notably improved with the addition of AR-BF composites. We also examined the solidification and leaching mechanisms of arsenic in the basalt glass system. BFs containing up to 0.4 mol% As2O3 exhibited arsenic leaching levels below the standard threshold (<67.7 μg/dm2) under strong acid/alkali immersion conditions. These results highlight the potential for in-situ curing and recycling of hazardous AR, particularly in the development of mechanically reinforced materials.