Multilayer thin films consisting of alternating layers of poly(chloro-p-xylylene) (PPXC) and silicon dioxide (SiO2) were deposited at 80-85 degrees C, taking advantage of a recently developed process to deposit SiO2 at near-room temperature by thermal chemical vapor deposition (CVD). The method used to deposit SiO2 is general and can be applied to near-room temperature deposition of many oxide thin films such as Al2O3, Y2O3, TiO2, ZrO2, Ta2O5, Nb2O5, and ZnO; but for the development of low dielectric constant materials to reduce RC-delay in ultra large scale integration (ULSI) devices, the deposition of SiO2 with a polymeric material is more applicable. Further, the ability to deposit SiO2 in a multilayer structure with a polymer is also advantageous to studying ultrathin polymeric films which finds applicability where polymeric materials experience confined geometry such as in composite materials, lubrication and biocompatible ultrathin films. X-ray diffraction (XRD) results showed the presence of new crystallites in the homopolymer film after post-deposition anneal at 150 degrees C due to a decrease in the d-spacing but after a 200 degrees C post-deposition anneal, only an increase in crystallinity occurred due the nucleation and growth of new crystallites and not the growth of existing crystallites. However, the multilayer films were more sluggish to crystallize and to form new crystallites after post-deposition anneals as compared to PPXC as a result of a thickness effect at similar to 35 nm. The introduction of a polymer with SiO2 raised the index of refraction from 1.44 to 1.59 (@630 nm) and lowered the dielectric constant from 4.0 to 3.30 (@10 kHz) with a PPXC thickness fraction of similar to 0.80.