Improvement of optical and electrical properties of borate glasses is a great demand for upgrading optoelectronic devices. Additionally, the transformation of borate glasses to nanostructured glass-ceramics endows them with outstanding beneficial properties to widen their application range. Herein, novel borate glass compositions are synthesized by the facile melt quenching method. The influences of V2O5-incorporation and nanocrystallization on the structural, optical, and electrical properties of the investigated cerium borate glasses are studied. The heat-treatment process promotes the precipitation of CeO2 and VCeO4 nanocrystals in the glass network. Linear and high dependence of the band gap of the as-prepared glasses on the V2O5 concentration is observed. A narrow band gap (about 1.6), which lies in the range of ideal bandgaps for two-junction photovoltaic cell applications, is achieved. Strong absorption in the visible and/or UV regions is attained for the studied samples, which is beneficial to shield laser emissions (up to 794 nm) and/or protect against the hazard of UV radiation. High DC conductivity (about 3 × 10-6 S/m) is approved for the glass sample containing V2O5 content of 10 mol%. The investigated glasses and nanostructured glass-ceramics are recommended as promising candidates for UV-protection sunglasses, laser safety, visible light irradiation photocatalyst, and next-generation semiconductors.