A photocatalytic HC/SCR system has been developed and its high deNOx performance (54.0-98.6% NOx conversion) at low temperatures (150-250 °C) demonstrated by using a representative diesel fuel hydrocarbon (dodecane) as the reductant over a hybrid SCR system of a photocatalytic reactor (PCR) and a dual-bed HC/SCR reactor. The PCR generates highly active oxidants such as O3 and NO2 from O2 and NO in the feed stream, followed by the subsequent formation of highly efficient reductants such as oxygenated hydrocarbon (OHC), NH3, and organo-nitrogen compounds. These reductants are the key components for enhancing the low temperature deNOx performance of the dual-bed HC/SCR system containing Ag/Al2O3 and CuCoY in the front and rear bed of the reactor, respectively. The OHCs are particularly effective for both NOx reduction and NH3 formation over the Ag/Al2O3 catalyst, while NH3 and organo-nitrogen compounds are effective for NOx reduction over the CuCoY catalyst. The hybrid HC/SCR system assisted by photocatalysis has shown an overall deNOx performance comparable to that of the NH3/SCR, demonstrating its potential as a promising alternative to the current urea/SCR and LNT technologies. Superior durability of HC/SCR catalysts against coking by HCs has also been demonstrated by a PCR-assisted regeneration scheme for deactivating catalysts.