A great interest exists to reduce power consumption, cross-talk, and RC-delay in ULSI devices by replacing SiO2(k=3.9−4.3) with a polymeric material (k<3.0). Unlike SiO2, polymeric thin films exhibit a complex morphology which varies with the polymer's thermal history, deposition temperature, and film thickness. Since the morphology of the polymer thin film ultimately affects its properties such as its dielectric constant, methods need to be developed to understand the morphological changes in polymer thin films. Further, the polymer thin films must exhibit a high thermal stability due to the relatively high back-end-of-line (BEOL) processing temperature. The polymers which exhibit high thermal stability often contain a mainchain benzene ring. Since benzene has a high anisotropic molecular polarizability, optical birefringence can be used to monitor the polymer chain conformation as a function of the polymer's thermal history, thickness or deposition conditions. Poly(p-xylylene) and poly(tetraflouro-p-xylylene) are shown to have a large negative birefringence, increasing until polymer decomposition. Poly(p-xylylene) becomes increasingly more negatively birefringent after a crystallographic phase change at 220°C. A high negative birefringence results in a large in-plane capacitance, negatively impacting the polymers potential benefit. owever, poly(chlorop-xylylene) and poly(dichloro-p-xylylene) exhibit positive birefringence, which increases until their crystalline melting points at ∼290°C and ∼380°C and thereafter decreases due to film disruption. Conclusions will be drawn based on this positive birefringence for the future molecular design of CVD polymers to decrease their in-plane dielectric constant. Urther poly(chloro-p-xylylene) and poly(p-xylylene) are investigated as a function of deposition temperature and film thickness.