Abstract A polypyrrole modified carbon-supported cobalt hydroxide (Co(OH) 2 -PPY-C) has been prepared by the impregnation-chemical method and used as the electrode catalyst in a direct borohydride fuel cell (DBFC). The microstructure of Co(OH) 2 -PPY-C has been characterized by X-ray diffraction and transmission electron microscopy. The cell performance and short-term performance stability of the DBFC using the Co(OH) 2 -PPY-C as catalysts have been investigated. A maximum power density of 83 mW cm −2 has been achieved at 0.6 V under ambient conditions. The Co(OH) 2 -PPY-C catalyst demonstrates a smaller value of polarization than the carbon-supported Co(OH) 2 catalyst. Results from electrochemical impedance spectrum analysis confirm that the polypyrrole addition to the cathode effectively decreases its resistance. During operation of the DBFC using Co(OH) 2 -PPY-C as catalyst, the Co(OH) 2 tends to be converted into CoHO 2 .