New cellular foam metals of various composition become widespread in recent years. They can be obtained by the injection on inert gases into the molten metal, or by stimulation of the local gas formation due to the introducing of gas-evolving chemicals (such as TiH2). The density of these materials is 0,35-0,7 g/cm3, they have high value of communicating channel porosity (80–97 %), and have no optically through channels. Under the conditions of liquids or gases flow, the intensive mass-transfer and mass-exchange is ensured. To use these materials as electrodes in the electrochemical redox-processes, the chemical-catalytic modification of their surface was applied, by plating of Ni-alloys with certain d-metals (Co, Mo, W, Re). It was shown that this process is auto-catalytic and makes it possible to ensure the high smoothness of the entire porous surface of foam metals. As a reducer, sodium borohydride (NaBH4) or dimethyl-borane ((CH3)2HN·BH3) was used, which allowed to obtain boron-containing coatings under the stable conditions. The mechanism of chemical-catalytic metal reducing is based on the catalytic effect of the reducer molecules oxidation (hydrolysis) stages, with the electrons transfer to the electrode surface, which shifts its potential to the values, sufficient for the running of the metal ions reduction reactions. Alloying of nickel with heavy polyvalent metals, especially with rhenium (with its optimal contents of 11 %), causes the reducing of hydrogen evolving reaction overvoltage by~200 mV in the acid and alkaline mediums within the currents range of 1,0-5,0 А/dm2. Compared to the electrode made of pure electroplated nickel, the reducing of hydrogen evolving reaction overvoltage for this alloy makes ~150-180 mV. For the electrodes made of Ni-B alloy, the value of Tafel coefficient (b) for hydrogen evolving reaction in the acid mediums makes 0,160 mV, whereas for the alloys with Re - 0,08 mV for acid mediums, and 0,166 mV – for alkaline ones. The exchange current values for hydrogen evolving reaction in the acid mediums for the electrodes made of electrochemical nickel make ~6·10-6 А/сm2, for alloy Ni-B ~6·10-4 А/см2, and alloys with rhenuim (11%) – around 7·10-3 А/см2, which is close to the current exchange values on Pt and Pd surface. In the alkaline solutions the exchange currents on the Ni-B electrodes make 3·10-8, and on Ni-Re-B electrodes (11 at.% Re) - 10-7 А/сm2. On the base of this research, the new methods of electrodes preparation for electrochemical processes have been proposed (MD patents № 244z, 3806, 4087). The studied characteristics of flow-through voluminous electrodes’ surface made it possible to propose their applications in the processes of oxidized ironing electrolytes regeneration (MD patents №№ 4432, 211z), and in water electrolysis processes for hydrogen generation (patent MD №№ 375z, 322z, 4109, 320z), which allow to reduce the energy consumption for these processes running.