A number of industrial electrochemical processes employ high surface area Ni electrodes. These include the use of Ni anodes in alkaline or molten carbonate fuel cells [1‐3], NiO(OH) cathodes in nickel‐cadmium and nickel‐hydrogen batteries [4] and hydrogen evolving Ni cathodes in alkaline water electrolysis [5] as well as in electrochemical hydrogenation of organics [6]. There are various types of high surface area Ni electrodes and an even larger variety of preparation methods. Sintered microporous Ni coatings are usually manufactured according to the ceramic foil-casting technology, by mixing of a micrometer size nickel powder with an organic binder, which is subsequently thermally decomposed with further sintering at elevated temperatures in a hydrogen atmosphere [3]. The methods for the production of nanoporous Raney‐Ni coatings include cold rolling, plasma spraying, annealing, sherardizing and cathodic codeposition of the Raney‐nickel precursor alloys (Ni/Al or Ni/Zn) on a nickel support [7]. PolyHIPE Polymer (PHP) [8, 9] is a microporous material produced through the formation of a high internal phase water-in-oil emulsion, in which the volume of the aqueous dispersed phase is greater than about 75%, and the subsequent polymerization (at 60 C) of the oil phase which contains the monomer (styrene and occasionally other monomers too) and the cross-linker (divinylbenzene). This results in the production of a porous polymer matrix due to the evaporation of the water droplets, which were present in the precursor emulsion. The structure of PHP is characterized by the presence of numerous cells (of 1‐100 lm diameter) interconnected by smaller pores (of 0:1‐10 lm diameter).We have recently reported the incorporation of Ni into the PHP matrix by electroplating through its pores and onto a thin Au layer electrode pasted on one side of a polymer sample [10] or onto a Ni mesh in a Ni/ PHP/Ni composite cell [11]. Thermal decomposition of the polymer resulted in a granular Ni structure of BET surface areas in the range of 1‐50 m 2 g ˇ1 depending on the method and plating current density. The main advantages of this process for producing nickel coatings of morphology comparable to that of sintered Ni are the inexpensive raw materials for the polymer matrix production and the relatively low temperature processing. Furthermore, the high surface area coating can be deposited on a variety of substrate electrode materials (e.g., stainless steel, reticulated vitreous carbon) and on substrates of diAerent geometries. The work presented here introduces a further modification of the technique, whereby only the Ni cathode wire is immersed into the precursor emulsion and finally entrapped into a well-defined PHP coating after polymerization. A preliminary characterization of the porous Ni coating, produced after electroplating and polymer decomposition, with respect to hydrogen evolution from alkaline solutions is also presented.