A novel poly(p-xylylene), PPX, derivative bearing alkoxyphenyl side groups was electrochemically synthesized in 87% yield. The polymer, poly(4′-hexyloxy-2,5-biphenyleneethylene) (PHBPE), presented a fraction (92%) soluble in common organic solvents. It showed to be thermally resistant up to 185°C. UV–vis analysis revealed an E gap of 3.5eV. Gas sensors made from thin films of 10-camphorsulfonic acid-doped PHBPE deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five VHOCs: 1,2-dichloroethane, bromochloromethane, trichloromethane, dichloromethane and tetrachloromethane. The conductance decreased after exposure to tetrachloromethane and increased after exposure to all the other VHOCs. Three-dimensional plots of relative response versus time of half response versus time of half recovery showed good discrimination between the five VHOCs tested.