Poly(p-xylylene) or parylene has been around for more than a half a century. It is typically deposited by the Gorham method from [2.2] paracyclophane. However, another method is via alpha-derivatives of p-xylene. Both poly(a-bromo-p-xylylene) and poly(a-chloro-p-xylylene) have been successfully deposited by this route through predominately HBr or HCl dehydrohalogenation gas-phase reactions. In the study reported here we synthesize a,a,a-tribromo-p-xylene and a-bromo-a′,a′-dichlorop-xylene as CVD precursors to yield a,a-and a,a′-dihalogenated poly(p-xylylene)s to try to convert them, via post-deposition annealing, to poly(phenylene ethynylene) (PPE). PPE and its intermediate poly(phenylene vinylene) (PPV), have potentially better thermal and oxidative properties, and in addition they are both photoluminescent. The as-deposited and annealed thin films have been characterized by Rutherford backscattering spectrometry (RBS), infrared spectroscopy, and UV-vis spectrophotometry, and electrically tested by dielectric constant, bias-temperature stress (BTS), and leakage current. It is found that the thin films crystallizes concurrent with the formation of PPV and possibly converts to PPE but has much residual chlorine and bromine. However, PPV exhibits excellent stability in contact with copper and is more thermally stable than poly(p-xylylene).