Ba₂Pb(B₃O₆)₂ polycrystalline powder was synthesized by a solid state reaction using BaCO₃, Pb₃O₄ and H₃BO₃ as initial reactants. The crystal structure was solved from the powder X-ray diffraction data by the Rietveld refinement method and the DFT (density functional theory) calculation. The results show that Ba₂Pb(B₃O₆)₂ is isostructural with the high-temperature phase BaB₂O₄ (Ba₂Ba(B₃O₆)₂). It crystallizes in the trigonal space groupR  $$c with a = b = 7.20295(3) Å, c = 37.594(1) Å, and Z = 6. The structure is built up of the layers of B₃O₆ rings that are separated by Ba²⁺ or Pb²⁺ cations. The Raman spectrum of Ba₂Pb(B₃O₆)₂ was interpreted on the basis of the analysis through site group method. Its irreducible representation of the normal modes is 10A_1g + 11A_2g + 10A_1u + 11A_2u + 21E_g + 21E_u among which 10A_1g + 11A_2g + 10A_1u + 10A_2u + 21E_g + 20E_u are optical modes, where the A_1g and E_gare Raman active. The DFT calculated results confirmed the results of the site group analysis and assigned all peaks in the experimental Raman spectrum. The α-BaB₂O₄Raman spectrum was recorded and compared with the Ba₂Pb(B₃O₆)₂ Raman spectrum. The effect of the Pb²⁺ cations on the Raman intensity was discussed.

Materials Chemistry and Physics, 2015