Sm3+/Eu3+ co-doped thermally stable potassium zinc alumino borosilicate glasses prepared by melt quenching method have been characterized by using spectroscopic techniques to understand their luminescence behavior. For an undoped glass, the XRD pattern recorded confirms the amorphous nature whereas FT-IR and Raman spectrum confirms the functional groups present. Addition of Sm3+ ions as a sensitizer makes the as prepared glasses more efficient for display devices. The mechanism of the energy transfer from Sm3+ to Eu3+ ion has been observed through non-radiative process. The non-exponential time decay curves are giving decreasing lifetimes with increase in Eu3+ ion concentration confirms the energy transfer. The calculated CIE points for the glasses move towards the red region with increase in the concentration of Eu3+ ions under the UV excitation. All the results obtained contemplate the suitability of the as prepared glasses for photonic device applications such as w-LEDs, solar cells and display devices.