Using first-principles calculations, this paper reports a systematic research on HER performance enhancing of LNS-TiO.sub.2 by passivated codoping. Six codoping systems, Ti.sub.17O.sub.35CrC, Ti.sub.17O.sub.35MoC, Ti.sub.17O.sub.35WC, Ti.sub.17O.sub.35VN, Ti.sub.17O.sub.35NbN and Ti.sub.17O.sub.35TaN are studied. Results show that the energy band can be tuned by the codoping donor-acceptor pairs. The energy band performance of Ti.sub.17O.sub.35WC should be the best in HER process for its tiny CBM change and small band gap. Besides, the hydrogen adsorption ability of LNS-TiO.sub.2 in HER process can also be tuned by the codoping pairs. The hydrogen adsorption performance of Ti.sub.17O.sub.35TaN should be the best for its âG.sub.H* is close to zero. In a word, Ti.sub.17O.sub.35WC and Ti.sub.17O.sub.35TaN have their own advantages as catalysts in HER process, and their exact HER efficiency is waiting to be obtained in the future experiments. In general, this passivated codoping LNS-TiO.sub.2 represents a novel kind of material. Research in this paper can enrich the theoretical knowledge of HER field.