 Bacterial cellulose (BC) was used as a raw material to produce freestanding carbon aerogels (CAs). The CAs were further decorated with Ni and MnO2/Ni(OH)2 hybrid via electrodeposition and redox reaction to produce carbon nanofiber networks decorated with electrochemically active metal and metal compounds. The properties of this novel material as supercapacitor electrodes were investigated. The electrochemical performance of the electrodes was examined in 1 M Na2SO4 electrolyte using cyclic voltammetry (CV), cyclic charge–discharge (CCD), and electrochemical impedance spectroscopy (EIS) tests. The results showed that a specific capacitance of 109 F g−1 was achieved at the current density of 1 A g−1. The electrodes could deliver an energy density of 9.4 Wh kg−1 and a power density of 4 KW kg−1 and demonstrated a high cyclability. These results showed great potential of this new material for supercapacitor electrodes. A flexible solid-state supercapacitor prototype was prepared using this material to demonstrate its function as a power source for a LED light. This study provided a new way to use BC as a biobased low-cost material for the fabrication of energy storage devices.