This paper demonstrates the results of constructive technological research on the development of a catalyst with a Ni/PSi@Pt structure. This catalyst eliminates the use of gold in the structure of μ-FC electrodes. This work uses the main technological solutions for the formation of a gold-containing “core–shell” structure on the inner surface of pores. Comparative data on the results of assessing the durability of porous silicon electrodes with both Pt catalysts and composite catalysts of the Pt/In₂O₃, Pt/SnO₂, Pt/Au and Pt/Ni types are also presented.