Samples of undoped and (Eu3+, Dy3+) ions co-doped BaCO3, were synthesized by autocombustion method. The samples nanostructures were characterized by various techniques such as X-ray diffraction, scanning electron microscopy (SEM), Photoluminescence (PL) spectroscopy and electron paramagnetic resonance (EPR). Based on XRD analysis, the undoped and (Eu3+, Dy3+) co-doped BaCO3 kept its orthorhombic structure. The calculated crystallite sizes for undoped and (Eu3+, Dy3+) co-doped BaCO3 samples are 70 and 49 nm, respectively. The FTIR spectra allowed the determination of the vibration modes of BaCO3. Morphological analysis showed that the synthesized powders consist of spherical and agglomerated particles. The EPR measurements exhibited a narrow response for BaCO3, along with an increased intensity in the case of the Eu3+ doped and (Eu3+, Dy3+) co-doped samples, indicating the incorporation of Eu3+ and Dy3+ ions into the matrix. The effect of Dy3+ (0.5 %) on the luminescence properties of BaCO3:Eu3+were studied. The results indicated that the lifetimes of the state 5D0 of Eu3+ increase from 1.15 to 1.31 ms in the presence of Dy3+, proving an energy transfer from Dy3+ to Eu3+ ions. This transfer was verified also by photoluminescence spectra, quantum efficiency of the 5D0 → 7F2 emission (80 %) and the emission cross section (39×10−22 cm2). The CCT (4239 K) and CRI (87) were calculated. Therefore, Eu3+, Dy3+ co-doped BaCO3 material could be used in the fields of w-LED applications.