Preferred crystallographic orientation (texture) in thin films of technologically important materials frequently has a strong effect on the properties of these films and is important for stable surface properties. The deposition of organized molecular films of a poly-perfluorodecylacrylate, poly-(1H,1H,2H,2H-perfluorodecyl acrylate) (p-PFDA), by initiated chemical vapor deposition (iCVD) is described. The tendency of p-PFDA to crystallize in a smectic B phase has been reported in films prepared from solution but not for those using a CVD technique. The degree of crystallinity and the preferred orientation of the perfluoro side chains, either parallel or perpendicular to the surface, are controlled by tuning the CVD process parameters (i.e., initiator to monomer flow rate ratio, filament temperature, and substrate temperature). Films with no observable X-ray diffraction patterns are also achieved. The observed differences in crystal texture strongly impact the observed water contact angles (150° to 130°, advancing) and corresponding hysteresis behavior. Low hysteresis (<7°) is associated with high crystallinity, particularly when the orientation of the crystallites resulted in the perfluoro side groups being oriented parallel to the surface. The latter texture resulted in smoother film than the texture with the chains oriented perpendicular to the surface and this can be very advantageous for applications in which relatively smooth but still crystalline films are needed.