The HgO-added YBa₂Cu₃O_7−δ (YBCO) superconductor has been studied for its structural and superconducting properties. Polycrystalline YBCO samples were synthesized through solid-state reaction method by adding HgO in different concentrations without using oxygen annealing. All the samples showed a sharp superconducting transition temperature around 90 K. The X-ray diffraction patterns of all the samples revealed monophasic Y-123 nature. The structural studies were carried out by neutron scattering and Rietveld analysis. The neutron scattering revealed that Hg is not incorporated in the Y-123 system and has shown optimum oxygen concentration. The significant role played by the HgO is to provide oxygen ambient through its decomposition, thus changing the oxygen balance in favour of high Cu-valence state.