The nearly monodispersed Pd nanoparticles with controllable density on ZnO nanorod arrays were prepared by the unique PVP-mediated photochemical deposition (PCD). The changes in morphology and dispersion of Pd on ZnO surface are ascribed to the stabilizing property and self-assembly characteristic of PVP being exploited during PCD. There are three temperature-dependent H(2) sensing mechanisms in those Pd/ZnO NRs, including general oxygen adsorption/desorption mode within 200-300 °C, surface conductivity mode at 60-120 °C and palladium hydride (PdH(x)) formation at room temperature, which causes a significant discrepancy in sensitivity variations as a function of Pd density. It is also verified that the electronic sensitization related to the transition of Pd(2+)/Pd(0) redox couple predominates the promoting mechanism in Pd/ZnO NRs used for sensing H(2) at 200-300 °C. Therefore, the gas sensitivity to 500 ppm H(2) of Pd/ZnO NRs can be significantly improved by around 553-fold (S, R(a)/R(g) = 1106) at 260 °C through decorating an adequate amount of discrete Pd nanoparticles instead of the Pd clusters, moreover, the corresponding sensitivity at room temperature is 16.9 that is superior to some promising devices reported in the literatures.