PS-PEO diblock copolymer and PEOX were synthesized. High ordered mono- and multi-layers of these materials could be transferred onto the single crystal silicon chips by the vertical dipping method using LB film (Langmuir-Blodgett film) techniques. The LB films surface pressure π-A isotherms were given. The topography and microtribological properties were studied using AFM/FFM(Atomic Force Microscope/Friction Force Microscope). The experimental results show that LB films of PS-PEO and PEOX have been well prepared and these mono- and multilayer films are high-ordered. Because of the good micro-tribological properties, further research of these materials on microtribology is essential.