Doping with noble metal nanoparticles (NPs) is an effective method to tune the photoluminescence (PL) properties of semiconductor materials. The mechanism is widely attributed to the localized surface-plasmon-resonance (SPR) effect of the metal NPs, while the contribution of potential barrier at the interface between metal and semiconductor is less discussed. Taking ZnO nanorods on fused silica substrates as a model system, we present a facile low-temperature fabrication method to derive Ag metal NPs coated ZnO nanorods. Great enhancement of the near-band-edge (NBE) ultraviolet emission of the ZnO nanorods was achieved by the surface decoration with Ag NPs, accompanied with a decrement of deep-level (DL) emission intensity. Since, the Ag NPs are active even at ambient conditions, spontaneous changes in PL properties have been observed with aging time. The influence of oxidation state of Ag on the contacting potential and subsequently on the PL properties of ZnO nanorods were studied by employing a subsequent thermal annealing process. The role of contacting behavior and the varied potential barrier are comprehensively discussed. It was demonstrated that both the SPR effect and band bending effect can enhance the NBE emission and suppress the DL emission. In the Ag-decorated ZnO nanorods, the SPR effect is the main reason for PL enhancement of the metallic silver, while the potential barrier enhancement is the main reason for the oxidized silver.