A series of highly ordered ladder-like polysilsesquioxanes (LPS) has been synthesized via ''stepwise coupling polymerization'' in recent years. Among them some Mew kind of reactive polymers, such as polyhydrosilsesquioxane, polyvinyl or allyl) silsesquioxane, polyethoxysilsesquioxane, etc. as parent polymers, can be further functionalized by hydrosilylation reaction as well as hydrolysis, thermal or photo-crosslinking and group-replacement reactions. New kinds of so-called ''fishbone-like'' and ''rowboat-like'' liquid crystalline polymers and their corresponding metal complexes have been prepared and used as promising skeleton material to form a polymer-network liquid crystal display film and electroconductive film. Other potential applications include: thermostable glass-like photopatternable film, insulation layer of semiconductor device, high-performance protective coating material on the surface of single crystal, lens or integrated circuit with excellent laser-damaged and environment resistance, organic/inorganic hybrid material supermolecular self-assemblies, low decay, second harmonic generation, nonlinear optical polymer or other orientation film, as well as polymeric solid electrolyte polymeric auxilary agent and so on. (C) 1997 by John Wiley & Sons, Ltd.