TiO2–Ag2O composite nanorods with various Ag2O configurations were synthesized by a two-step process, in which the core TiO2 nanorods were prepared by the hydrothermal method and subsequently the Ag2O crystals were deposited by sputtering deposition. Two types of the TiO2–Ag2O composite nanorods were fabricated; specifically, discrete Ag2O particle-decorated TiO2 composite nanorods and layered Ag2O-encapsulated TiO2 core–shell nanorods were designed bycontrolling the sputtering duration of the Ag2O. The structural analysis revealed that the TiO2–Ag2O composite nanorods have high crystallinity. Moreover, precise control of the Ag2Osputtering duration realized the dispersive decoration of the Ag2O particles on the surfaces of the TiO2 nanorods. By contrast, aggregation of the massive Ag2O particles occurred with a prolonged Ag2O sputtering duration; this engendered a layered coverage of the Ag2O clusters on the surfaces of the TiO2nanorods. The TiO2–Ag2O composite nanorods with different Ag2O coverage morphologies were used as chemoresistive sensors for the detection of trace amounts of NO2 gas. The NO2 gas-sensing performances of various TiO2–Ag2O composite nanorods were compared with that of pristine TiO2 nanorods. The underlying mechanisms for the enhanced sensing performance were also discussed.