Poly(chloro-p-xylylene) thin films are shown to have a changing morphology as a function of deposition temperature from spectroscopic ellipsometry and X-ray diffraction measurements. At lower deposition temperatures, the as-deposited polymer exhibited negative birefringence attributed to the presence of amorphous conformationally disordered polymer chains. As the deposition temperature was increased the polymer chains became more conformationally ordered resulting in an increase in the thin film's birefringence. At higher deposition temperatures, above the polymer's T-g evidence of crystallinity was apparent from X-ray diffraction results. The increase in the thin film's birefringence may be attributed to the thermodynamic driving force for crystallization causing the plane of the phenyl group to orient more perpendicular to the plane of the substrate, evidently the more stable conformation for poly(chloro-p-xylylene). After an inert post-deposition anneal at 210 degrees C for 2 h, the thin films deposited at lower temperatures showed evidence of higher crystal quality than the above T-g deposited films because of a smaller d-spacing. A decrease in the full width half max of the X-ray diffraction peak was attributed to a large increase in the crystallite size, larger for the films deposited at higher temperatures as a result of a greater degree of crystallinity present in those films as deposited. Further, comparisons are made between the as-deposited and post-deposition annealed samples in terms of stress, crystalline disorder and crystallite size. In addition, from differential scanning calorimetry measurements, the glass transition temperature of poly (chloro-p-xylylene) was 35 degrees C-36 degrees C and 44 degrees C at heating rates of 0.2 degrees C/min and 5 degrees C/min.