The Co3O4 nanorods (NR-Co3O4) electrode is synthesized by using a calcination-process assisted hydrothermal method. Each Co3O4 nanorod possesses porous structure with well-defined nanoparticles. The unique NR-Co3O4 electrode exhibits the superior electrochemical performances, including a specific capacity of 1272 C g(-1) at a current density of 1.89 A g(-1) and 90.3% of capacity retention after 18,000 cycles at 23.58 A g(-1). The NR-Co3O4//active carbon (AC) device is also assembled to probe the virtues of NR-Co3O4 electrode, manifesting a maximum energy density and power density of 55.4 Wh kg(-1) and 4490 Wkg(-1), respectively. Amazingly, the NR-Co3O4//AC device exhibits the super-long cycling stability with 90.4% retention ratio after 36,000 cycles. Furthermore, an energy harvesting-storage system is constructed by integrating the commercial solar panel with the power package composing of four NRCo3O4// AC devices in-series, witnessing the fast photo-charge and discharge capability of NR-Co3O4//AC device. These facts strongly demonstrate the synthesized NR-Co3O4 is promising towards the practical application for self-powered technology in future.