La2CaB10O19 powders doped with Eu3+ ions were synthesized using a citric route for the first time. The La2CaB10O19 powders doped with Eu3+ ions were synthesized using citric route for the first time. The crystal structure, morphology and chemical composition of the engineered compounds were characterized in details using X-ray diffraction (XRD), Raman spectroscopy, transmission and scanning electron microscopy (TEM and SAED) and X-ray fluorescence (EDX). The photoluminescence properties (emission, excitation, excited state dynamics) were evaluated in the temperature range 300-700 K. We have found that the thermal dependency of Eu3+ emission is quite complex in LCBO. Four different temperature zones were found as well as contribution of a second emitter at higher temperature. The thermal quenching mechanisms of Eu3+ luminescence in this host lattice are addressed.