Copolymerization of chemically vapor deposited poly(p-phenylenevinylene) and parylene-N is explored as a method for color-tuning the polymer photoluminescence. A significant blue shift in peak photoluminescence from that of pristine poly(p-phenylenevinylene) is observed in the vapor-deposited copolymer, the magnitude of which is controlled by the delivery rates of each of the monomers, with peak photoluminescence wavelengths ranging from 525 nm for low parylene-N incorporation to 470 nm for high parylene-N incorporation. These copolymers are successfully integrated into single-layered light-emitting diodes exhibiting blue light output, which is the first demonstration of color-tuning poly(p-phenylenevinylene) prepared by parylene-based chemical vapor deposition.