A porous polypyrrole (PPy) material having a three-dimensionally developed, continuous porous structure was fabricated by using a polyacrylonitrile (PAN) monolith as a template. The PAN monolith was easily produced through a thermally induced phase separation approach. Electroconductive Au/PAN monolith was prepared by electroless Ni plating and substitution plating for Au in order to use a PAN monolith as a template electrode for the electrodeposition of PPy. Then a PPy/Au/PAN monolith was prepared by the template electrodeposition of PPy on the Au/PAN monolith template electrode. PPy was found to be uniformly deposited on the entire template electrode, including its inside. Cyclic voltammetry experiments revealed that the PPy/Au/PAN monolith exhibited much higher electrochemical capacitance due to its porous structure. This new material could potentially be used in energy device applications such as capacitors and batteries.