Self-assembled nanometer-sized stripes are obtained spontaneously by electrostatic adsorption of bolaform amphiphiles bearing hydrophilic :pyridinium headgroups and rigid hydrophobic azobenzene onto mica sheets. The ordered stripes have a repeat spacing of 10 nm, and the ordered region can extend over: macroscopic areas. The formation of such nanostructures mainly depends on the concentration of the bolaform amphiphiles. The template effect of the mica sheet also plays a crucial role in the molecular organization at the Liquid solid interface. The degree of order of the stripes is influenced by adding electrolyte into the aqueous solution or upon irradiating the solution for physical adsorption under UV light.