A method of vapor deposition polymerization with thermal and photochemical initiation was applied to aromatic diazides to obtain thin films of conjugated azo-aromatic polymers. The chemical background, experimental device and operation flow chart are presented. Ten azides were tested but those of biphenyl and stilbene only let to films of high content of azo groups. Excepting 4,4’-diazidobenzophenone, the films were constituted of polymer networks with branching points and ends of amine type. Surface morphology, photoconduction and chemo-chromatism are the characteristics which were evidenced and investigated for the films of high content of azo structure.