We report on the morphology control and electroluminescence of well-aligned ZnO nanorod/p-GaN heterojunctions prepared by an aqueous solution route at low temperature (90 °C). We found that the density and size of the grown nanorods and microrods depended significantly on the ZnO seed density. Synchrotron X-ray scattering measurements showed an epitaxial relationship between the ZnO nanorods and the p-GaN thin film. ZnO nanorod/p-GaN heterojunction light-emitting diodes (LEDs) with an individual chip size of 300 × 300 μm2 were fabricated. Room-temperature electroluminescence spectra in the visible range were obtained from the LED at forward bias voltage. This result indicates that such heterojunction LEDs fabricated from solution are a promising approach for realizing large-area light-emitting sources that have high external quantum efficiency.