30Li₂O–55B₂O₃–5ZnO-7.5TiO₂-2.5V₂O₅ (mol%) glass is heat treated at different temperatures and durations to study the growth of nanocrystalline phases and their effect on various properties. X-ray diffraction (XRD) confirmed the crystallization of the nano-Zn₄O(BO₂)₆, LiV₆O₁₃ and Li_0·74(Ti₃O₆) phases along with glass matrix. Photoluminescence emission spectrum also confirmed the crystallization of nanostructured Zn₄O(BO₂)₆ in the glass matrix. The glass ceramics contain various borate groups as observed in Fourier transform infrared (FTIR) spectra. The optical band gap of glass-ceramics lies in the range of 3.46–3.56eV. Fast and maximum degradation efficiency (72%) is observed for organic methylene blue dye for glass heat-treated at 520 °C for 10 min. The present nanocrystalline glass-ceramics could be good photocatalysts with higher thermal stability and inertness than polymeric/ceramic capped nanocrystalline photocatalysts. The present method could pave an alternative and efficient way to degrade the organic substances in UV–Visible light without using any capping agent.