AbstractPolypyrrole (PPy)/cellulose (PPCL) composite papers were fabricated by vapor phase polymerization. Importantly, the vapor-phase deposition of PPy onto cellulose was assisted by employing different co-vapors namely methanol, ethanol, benzene, water, toluene and hexane, in addition to pyrrole. The resulting PPCL papers possessed high mechanical flexibility, large surface-to-volume ratio and good redox properties. Their main properties were highly influenced by the nature of the co-vaporized solvent. The morphology and oxidation level of deposited PPy were tuned by employing co-vapors during the polymerization, which in turn led to change in the electrochemical properties of the PPCL papers. When methanol and ethanol were used as co-vapors, the conductivities of PPCL papers were found to have improved five times, which was likely due to the enhanced orientation of PPy chain by the polar co-vapors with high dipole moment. The specific capacitance of PPCL papers obtained using benzene, toluene, water and hexane co-vapors was higher than those of the others, which is attributed to the enlarged effective surface area of the electrode material. The results indicate that the judicious choice and combination of co-vapors in vapor-deposition polymerization (VDP) offers the possibility of tuning the morphological, electrical and electrochemical properties of deposited conducting polymers.