This paper reports on high-quality InN materials prepared on a GaN template using radio-frequency metalorganic molecular beam epitaxy. We also discuss the structural and electro-optical properties of InN nanorods/films. The X-ray diffraction peaks of InN(0002) and InN(0004) were identified from their spectra, indicating that the (0001)-oriented hexagonal InN was epitaxially grown on the GaN template. Scanning electron microscopic images of the surface morphology revealed a two-dimensional growth at a rate of approximately 0.85 μm/h. Cross-sectional transmission electron microscopy images identified a sharp InN/GaN interface and a clear epitaxial orientation relationship of [0001]InN // [0001]GaN and ( 2¯110)InN // ( 2¯110)GaN. The optical properties of wurtzite InN nanorods were determined according to the photoluminescence, revealing a band gap of 0.77 eV.