Electrolysis is the process by which ionic substances or any solution are decomposed and broken down into simpler substances when an electric current is passed through them. For electrolysis to work, the ions must be free to move. Ions are free to move when an ionic substance is dissolved in water or when melted.
An aqueous solution of NaCl is more ionic than pure water. Hence, an aqueous solution of NaCl is a better conductor than pure water.