Cathodic evolution of hydrogen on the electrodes from sodium tungsten bronzes was studied. Great dependence of cd on time and prepolarization of the electrode is caused by absorption of atomic hydrogen in the electrode; this process is controlled by hydrogen diffusion in bronze. Mechanism of hydrogen evolution in sulphuric acid solutions was proposed on the basis of polarization curves, the dependence of overvoltage on the activity of hydrogen ion and anodic chronopotentiometric curves. The rate of hydrogen evolution is controlled by the reaction of electrochemical desorption of atomic hydrogen, the adsorption of which is fast and obeys Langmuir isotherm. Exchange cd of hydrogen evolution is of the order 10 −7 to 10 −6 A cm −2 and increases with the increase of sodium content in the bronze.