Highly crystalline ZnO nanorods with diameters ranging from 5 to 57 nm were prepared by a seed-mediated solution method. With a diameter reduction, the lattice volume of ZnO nanorods increased and c/a ratio decreased, in apparent contradiction to what was observed in spherical ZnO nanocrystals. All ZnO nanorods showed a strong yellow emission without the UV or green emissions that had been observed for ZnO nanostructures prepared by other methods. For larger diameters, the yellow emission exhibited an abnormal red shift, which was associated with the lattice variations in the nanoscale structure and the resulting band modifications. The size-induced band modifications were also confirmed by the photocatalytic activity of ZnO nanorods, which have an optimum diameter (approximately 30 nm) for the photodegradation of Rhodamine B dye solution.