Carbon nanofibres (CNFs) and tungsten oxide (W18O49) nanowires have been incorporated into a continuous flow type microplasma reactor to increase the reactivity and efficiency of the barrier discharge at atmospheric pressure. CNFs and tungsten oxide nanowires were characterized by high-resolution scanning electron microscopy, transmission electron microscopy and nanodiffraction methods. Field emission of electrons from those nanostructures supplies free electrons and ions during microplasma production. Reduction in breakdown voltage, higher number of microdischarges and higher energy deposition were observed at the same applied voltage when compared with plane electrodes at atmospheric pressure in air. Rate coefficients of electron impact reaction channels to decompose CO2 were calculated and it was shown that CO2 consumption increased using CNFs compared with plane electrode in the microplasma reactor.