Glass lead free sample of composition 10BaTiO3–60V2O5–30B2O3 in mol% was prepared by conventional melt quenching technique. The as-prepared sample shows relaxor ferroelectric-like behavior which is a novel phenomenon in the field of glass science. XRD and DSC were used to emphasize the glassy nature of the present sample. Diffraction spots from clusters are clearly observed using HRTEM, which is presumably from polar clusters (PCs). The sample shows a broad and diffuse peak in the temperature dependence of dielectric permittivity ɛ` (T) and tangent loss, the temperature of which increases with increasing measuring frequency, denoting the typical relaxor behavior. The existence of distorted BaTiO3 PCs embedded in the glass matrix is responsible for the appearance of this behavior. The present glass sample shows energy storage density of about 0.11 J/cm3 at room temperature and 0.44 J/cm3 at 120 °C, which is reasonably good for bulk polar material. The results obtained in this work could lay the basis for the development of lead free materials to meet the energy storage and Eco-friendly applications.