We report a new layer-by-layer growth method of self-assembled organic multilayer thin films based on gas-phase reactions. In the present molecular layer deposition (MILD) process, alkylsiloxane self-assembled multilayers (SAMS) were grown under vacuum by repeated sequential adsorptions of C= C-terminated alkylsilane and titanium hydroxide. The MLD method is a self-limiting layer-by-layer growth process, and is perfectly compatible with the atomic layer deposition (ALD) method. The SAMS films prepared exhibited good thermal and mechanical stability, and various unique electrical properties. The MLD method, combined with ALD, was applied to the preparation of organic - inorganic hybrid nanolaminate films in the ALD chamber. The organic - inorganic hybrid superlattices were then used as active mediums for two-terminal electrical bistable devices. The advantages of the MLD method with ALD include accurate control of film thickness, large-scale uniformity, highly conformal layering, sharp interfaces, and a vast library of possible materials. The MILD method with ALD is an ideal fabrication technique for various organic - inorganic hybrid superlattices.