The behavior of the polypyrrole (PPy) fibrils modified electrode during hydrogen evolution process is reported. The experimental results show that the hydrogen evolution current density could be significantly increased on the PPy fibrils modified electrode. The hydrogen evolution current density on the modified electrode increases with PPy fibrils getting longer. The hydrogen evolution current density on fibrillar PPy modified electrode is higher than that on electrode modified with PPy with cauliflower form. Redoping PPy fibrils with metal complex could further increase the hydrogen evolution current density.