Nanoporous cobalt oxide nanorods were synthesized by a hydrothermal method. Transmission electron microscopy analysis showed that the individual Co3O4 nanorods have a nanoporous structure, consisting of the textured aggregations of nanocrystals. Optical properties of Co3O4 nanorods were characterized by Raman and UV−vis spectroscopy. Magnetic property measurement shows that Co3O4 nanorods have a low Néel transition temperature of 35 K. We observed quite significant exchange bias for nanoporous Co3O4 nanorods, indicating the existence of magnetic coupling between the nanocrystals in Co3O4 nanorods. When applied as electrode materials in supercapacitors, Co3O4 demonstrated a high capacitance of 280 F/g.