PbSO4 powders and crystals are prepared using gel growth, and their chemical and phase compositions are determined. The luminescence spectra of the crystals are measured between 10 and 300 K under excitation with 5- to 40-eV synchrotron radiation, the excitation spectra of the UV and blue emission bands are obtained, and the temperature effect on the emission decay is examined. The luminescence spectra show bands at 340 and 380 nm, which experience strong thermal quenching and arise from different emission centers. Increasing the temperature from 10 to 300 K accelerates the luminescence decay by three orders of magnitude, bringing it to the nanosecond range. Under gamma excitation in the range 122–1332 eV, the average room-temperature light output of the PbSO4 crystals exceeds that of Bi4Ge3O12 by 20%, with emission decay times τ1 = 1.85 ns, τ2 = 14.5 ns, and τ3 = 125–150 ns.