It is commonly recognized that the ionic conductivity of pure water is very poor because of very low ionic concentrations. However, this work indicates that pure water in charged porous matrixes can be moderately conductive because of the ions in the electric double layer established at the solid/water interfaces. The ionic conductivity of pure water in a charged matrix changes with the electrode potential of the matrix and is influenced by the structural parameters. Both experimental measurements and theoretical calculations reveal that ionic conductivity may reach the order of 10−3 S cm−1 in commonly accessible potential region in a porous matrix made of gold nanoparticles. These results would help to understand and optimize the electrode processes in electrochemical devices without deliberately added electrolytes, such as polymer electrolyte membrane fuel cells.