Doping and novel metallic nanoparticles loading on the photocatalyst are two effective means to enhance its photocatalytic activity. In our study, Pd-0/Pd2+-co-modified ZnWO4 nanorods were fabricated by a two-step hydrothermal process and room-temperature reduction method. The performance of the as-prepared samples was evaluated through the photocatalytic nitric oxide (NOx) removal under simulated solar and visible-light irradiation. Pd-0/Pd2+-co-modified ZnWO4 nanorods present a significantly enhanced photocatalytic activity for NOx removal compared with Pd-0-loaded or Pd2+-doped ZnWO4 under simulated sunlight irradiation owing to a narrower band gap of Pd2+ doping compared with that of pure ZnWO4. The role of Pd-0 nanoparticles is to act as an electron reservoir to restrain the recombination of e(-)/h(+) pairs. According to the trapping measurements, the photoinduced holes and electrons play critical roles during the photocatalytic process. In addition, electron spin resonance (ESR) results further confirm that O-center dot(2)- and (OH)-O-center dot radicals are present and assist in the photocatalysis under simulated solar light irradiation. Stability test demonstrated that 1.5% Pd-0/0.5% Pd2+-co-modified ZnWO4 nanorods as photocatalyst have high photocatalytic stability in NOx removal. This work proved that Pd-0/Pd2+-co-modified ZnWO4 nanorods can be considered as an efficient photocatalyst for NOx removal.