Based on the LiLaTiO3 compound, a ceramic membrane for a photoelectrochemical cell was created. The microstructure, phase composition, and conductivity of a semiconductor photoelectrode and a ceramic membrane were studied by using various experimental methods of analysis. A ceramic Li conducting membrane that consisted of Li0.56La0.33TiO3 was investigated in solutions with different pH values. The fundamental possibility of creating a photoelectrochemical cell while using this membrane was shown. It was found that the lithium-conductive membrane effectively works in the photoelectrochemical system for hydrogen evolution and showed a good separating ability. When using a ceramic membrane, the pH in the cathode and anode chambers of the cell was stable during 3 months of testing. The complex impedance method was used to study the conductive ceramic membrane in a cell with separated cathode and anode chambers at different pH values of the electrolyte. The ceramic membrane shows promise for use in photoelectrochemical systems, provided that its resistivity is reduced (due to an increase in area and a decrease in thickness).