A method is provided for the preparation of an electrode substrate for use in a liquid display device utilizing perpendicular alignment of liquid crystal and dichroic dye molecules. In the improved method, a base substrate bearing an electrode film is coated with an insulating film on the surface which contacts the liquid crystal. The insulating film is rubbed with cloth in a fixed direction and following the rubbing treatment, the rubbed surface is treated with a silane surfactant so that when the electrode substrate is employed in a liquid crystal display device, the liquid crystal and dye molecules are arranged in the direction of the major axes thereof in substantially perpendicular orientation at constant tilt angles in the same direction on the interface with said electrode substrate.