Eu3+-doped and Li+/Na+ co-doped K3Y(BO2)6 (KYBO) phosphors were synthesized through a microwave-assisted sol–gel method, and their structural and photoluminescent (PL) characteristics were examined. X-ray diffraction (XRD) and Rietveld refinement confirm effective dopant incorporation and preservation of the crystalline structure. Fourier Transform Infrared (FTIR) spectroscopy indicates the maintenance of the borate structure, confirming the structural integrity of the phosphors upon doping. The addition of Li+ and Na+ co-dopants notably enhances luminescent efficiency and thermal stability, making these phosphors promising candidates for solid-state lighting (SSL) applications. PL analysis reveals strong red emission peaks at 612 nm, attributed to the 5Do → 7F2 transition of Eu3+ ions. The study indicates that electric dipole-quadrupole interactions are the primary mechanism for energy migration, with a critical distance of approximately 22.68 Å. This mechanism contributes to concentration quenching at higher doping levels. High temperature PL measurements indicated an activation energy of 0.1389 eV for thermal quenching in the Li+ co-doped sample. Additionally, the Na+ co-doped sample exhibited an abnormal thermal stability behavior, with an even higher activation energy of 0.2536 eV. This suggests that Na+ co-doping significantly enhances the thermal resilience of the phosphor, making it more suitable for high-power light-emitting applications that operate under extreme conditions. CIE chromaticity diagrams highlight the potential for optimizing Eu3+ doping levels, combined with Li+ and Na+ co-doping, to improve luminescent performance and thermal stability for advanced SSL applications.