TiO2-doped carbon aerogels (CAs) were synthesized by sol–gel polymerization of a mixture of resorcinol, formaldehyde and tetrabutyl orthotitanate, followed by gelation and supercritical drying and carbonization in N2 gas atmosphere. The morphology of these TiO2-doped CAs was characterized by transmission electron microscopy. X-ray diffraction and Brunauer–Emmett–Teller methods were employed to determine the microstructure and surface characteristics of samples. It was found that the doped TiO2 had no significant effect on the surface area of the samples, whereas the pore and mesopore volumes were increased by the addition of TiO2. The TiO2 particles were kept still as anatase in samples carbonized at 900 °C, and did not transform into rutile on heating. Electrochemical performance of the samples as electrode materials was studied by cyclic voltammetry, electrochemical impedance spectroscopy, and constant current charge/discharge measurements. The results showed that the specific capacitance of CA electrodes had been improved by TiO2 doping, and the samples with wider pore diameters have higher capacitance values.