Low-cost resorcinol formaldehyde (RF) organic aerogels were prepared by using resorcinol and formaldehyde as precursors, and sodium hydroxide as a catalyst through a single-mode microwave radiation-assisted sol-gel method and ambient temperature drying. Because of the ring focusing and power-max technology, the fabrication procedure of carbon aerogels (CAs) are much easier, faster, and cheaper than traditional methods. The RF aerogels were then pyrolysized at 900 °C, and the KOH activation process was used to further dredge micropores in the carbon aerogels. The CAs were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption/desorption, and a series of electrochemical tests. The KOH activated carbon aerogels with 3D-nano-network structure exhibited a high specific surface area of 2230 m2 g−1 with appropriate pore volumes of micro-, meso-, and macropores. The specific capacitance of CAs activated by KOH measured in a two-electrode cell was 170 F g−1 at 0.5 A g−1 with excellent rate capability and cycle stability in 6 M KOH electrolyte.