A study was made of the solid-state polymerization of built-up monomolecular layers of vinyl stearate. Polymerization was initiated by exposing the samples to ⁶⁰Co γ-radiation. The reactions were followed by multiple internal reflection infrared spectroscopy. The structure of the multilayer monomer and polymer was studied by x-ray diffraction. Surface properties of the multilayers were studied by contact-angle measurements. Results showed that, under the proper conditions, monomer multilayers of vinyl stearate could be polymerized to virtually 100% completion. Reaction was favored by higher irradiation temperatures, larger doses of radiation, and by higher reaction temperatures. The x-ray diffraction photographs indicated that both the monomer and polymer multilayers possessed some single crystal character. Contact-angle measurements indicated that the molecules in both the monomer and polymer multilayers were closely packed.