The study proposes the utilization of microwave-assisted methods for converting neutralization slag (NS) into hydroxyapatite (HAP), offering an alternative to the conventional hydrothermal method. The microwave-assisted approach addresses the challenges encountered in hydrothermal reactions, such as particle agglomeration, reduced specific surface area, prolonged reaction time, high temperature requirements, and inadequate saturation adsorption capacity. By employing the response surface methodology with a Box-Behnken design, the study found that the microwave-assisted method significantly reduced the synthesis time from 90 to 25 min and the temperature from 120 °C to 56 °C. Furthermore, the microwave method consumed only 1/43 of the energy utilized in hydrothermal synthesis. To assess the performance of the synthesized HAP, various detection methods were utilized, including XRD, SEM-EDS, FTIR, Zeta potential, and ICP, which analyzed the crystal structure, crystallinity, morphology, chemical composition, and surface charge of HAP. The BET method was used to measure the specific surface area, further confirming the successful synthesis of HAP. The HAP synthesized through this microwave-assisted method exhibited a saturation adsorption capacity of up to 98.4 mg/g of fluoride ions from vanadium industrial raffinate. This study demonstrates that the microwave-assisted method provides a viable solution for reducing energy consumption and enhancing HAP synthesis efficiency for wastewater treatment in the vanadium industry.