Quantum and kinetic studies of novel materials based on parylene polymers and variously substituted vinyl molecules are presented and discussed. It is demonstrated that the thin films which are the products of the copolymerization reactions can be prepared (i) within the parylene CVD process on active vinyl substrates or (ii) employing the same process but involving an additional source of vinyl molecules transported to the reaction chamber. Both methods lead to differently functionalized microstructures, primarily dominated by the parylene units, while the vinyl molecules appear relatively seldom (depending on the nature of the substituents used). The copolymerization is shown to be independent of penultimate monomers in linear chains and to undergo composition drift within certain scope. Namely, it is found that even a small amount of p-xylylene monomers in feed leads to the formation of long blocks of pure parylene while the substituted vinyl molecules are expected to appear occasionally in chains. Finally, it is predicted that the two types of parylene functionalization result in specific structures and thus behavior of the corresponding thin films.