Porous carbons with controllable and narrow pore-size distributions are prepared from the chemical activation of polyfurfuryl alcohol (PFA). High apparent BET surface areas, up to 2600m2 g−1 (2611m2 g−1 by Density Functional Theory (DFT)), and good electrical conductivities (up to ∼130Scm−1) are obtained. By varying the potassium hydroxide: carbon precursor ratio, the preparation of carbons with different proportions of micro- and fine mesoporosity (<5nm) can be tailored to provide an ideal electronic and ionic pore structure for electrochemical energy-storage devices, such as electrical double-layer capacitors. High specific capacitance values are obtained up to 147Fg−1 in a voltage window of 2.5V using 1M tetraethyl ammonium tetrafluoroborate in acetonitrile. Moreover, excellent high-current and high-frequency performance is demonstrated: 100Fg−1 at 225Ag−1 (10Hz) and ∼30Fg−1 at 100Hz. When comparing the performance with commercial activated carbons (ACs) of similar textural properties, the PFA-derived ACs demonstrated better performance in terms of higher capacitance values and improved rate capabilities. There is a 125% increase in capacitance values at 1kHz.