Oxidative coupling of methane to higher hydrocarbons was investigated using two types of semiconductor catalysts, NbO (p-type) and Nb2O5 (n-type) at 1 atm pressure. The ratio of methane partial pressure to oxygen partial pressure was changed from 2 to 112 and the temperature was kept at 1023 K in the experiments conducted in a cofeed mode. The results indicated a strong correlation between C-2+ selectivity performance and the electronic properties of the catalyst in terms of p- vs. n-type conductivity. The p-type semiconductor catalyst, NbO, had a larger selectivity (e.g. 95.92%) over the n-type Nb2O5 catalyst (23.08%) both at the same methane conversion of 0.64%. Catalyst characterization via X-ray diffraction, TGA and reaction studies indicated that NbO was transformed to Nb2O5 during the course of the reaction which limits catalyst life.