Carbon aerogels derived from organic sol-gel process and supercritical drying are novel porous materials with interconnect structures and higher electrical conductivity, which are considered to be ideal electrode materials for supercapacitors and rechargeable batteries. The objective of the research was to synthesize carbon aerogel films at ambient conditions. Resorcinol formaldehyde (RF) and carbon aerogel films have been produced with extremely high RC ratio (molar ratio of resorcinol to catalyst) followed by subcritical drying. The structure of the porous films was investigated using electron scanning microscope. The specific surface area was measured by using nitrogen adsorption (BET) and electrical conductivity was measured with four-probe method. It was found that with extremely high RC ratio, the porous structure of RF and carbon aerogel films can be controlled from micro to macro porous at ambient conditions. With respect to the application as electrodes for fuel cells, carbon aerogel films with different porous structures on the two surfaces have been also obtained through optimizing the sol-gel process.