The spectroscopic exploration of Dy³⁺/Er³⁺/Sm³⁺ singly, doubly and triply doped BaO + ZnF₂+K₂O + SiO₂+B₂O₃ glasses have been carried out through photoluminescence excitation and emission, decay profiles, CIE color co-ordinates and correlated color temperature (CCT) values. Co-occurrence of Dy³⁺, Er³⁺ and Sm³⁺ luminescent bands in the fluorescence spectra of Dy³⁺/Er³⁺/Sm³⁺ triply doped multicomponent borosilicate glasses with different excitation wavelengths (348, 374, 379 and 400 nm) emphasizes the existence of energy transfer processes and is studied in detail. The luminescence intensity of Er³⁺ and Sm³⁺ bands has shown a remarkable reduction with the increase in Dy³⁺ content, whereas Dy³⁺ bands seemed to be enhanced monotonously. Luminescent kinetics of as-prepared samples were investigated thoroughly by using recorded decay profiles and the observed decrement in lifetime values validated proposed Er³⁺ (or Sm³⁺) to Dy³⁺ energy transfer routes. The energy transfer efficiency was considerably increased with the increase in concentration of Dy³⁺ ions and is substantially interpreted using partial energy level diagrams. The estimated CCT values and CIE color co-ordinates of the prepared samples were significantly changed from reddish-orange to warm white light and it suggests the suitability of the material for lighting applications.