Deep surface trap states present in hydrothermally grown ZnO nanorod (NR) arrays are monitored by photoelectrochemical and impedance spectroscopy. NR arrays were grown on a thin compact ZnO film deposited by pulsed laser deposition. Photocurrent responses upon square-wave illumination and lock-in detection of the as-grown NR arrays in the presence of Na2SO3 at pH 10 were characterized by a complex potential dependence indicating the presence of deep trap states. At a given frequency of light perturbation, the photocurrent amplitude increases as the potential bias is shifted towards values more positive than the flat band potential. Increasing the potential further than 0.8 V positive to the flat band potential leads to a decrease in the photocurrent amplitude. The potential of maximum photocurrent amplitude overlaps with a sharp decrease in the interfacial capacitance. The dependence of the photocurrent amplitude on bias potential strongly suggests the presence of deep electron trap states. The effect of the deep trap states are minimized by annealing of the NR arrays in air at 340° C.