Titanium carbides, oxides, nitrides and carbonitrides possess many special and excellent properties. But the high production cost caused by the traditional carbothermic reduction process severely limits the wide applications. In this study, a novel synthesis process has been proposed by reducing and carbonitriding TiO2 with CH4-H2-N2 gas mixture at low temperatures. The synthesis of Ti(C, N, O), reaction mechanism and the products composition have been investigated. Thermodynamic analysis indicated that TiO2 could be ultimately reduced and carbonitrided to Ti(C, N, O) by CH4-H2-N2 gas mixture. Based on the predictions of thermodynamics, the effects of reduction time, temperature, and gas composition have been studied experimentally. The obtained results indicated that increasing reduction temperature and introduction of N2 are beneficial to the synthesis of Ti(C, N, O). Finally, the optimum reaction conditions have been obtained. The density functional theory (DFT) results further demonstrated the reaction mechanism. This work provides a new approach to prepare metallic carbonitrides from their oxides.