The behavior of alloys of the Cu–Pd- and Ag–Pd-systems in the hydrogen evolution reaction in 0.1 M KOH aqueous solution is investigated. The role of copper and silver in the processes of the atomic hydrogen insertion and ionization is revealed. The mechanism of the hydrogen evolution reaction in aqueous alkaline solution on Cu,Pd- and Ag,Pd-alloys with the electronegative component content up to 60 at % is proposed. The limiting stage of the hydrogen evolution reaction on the palladium alloys in 0.1 M KOH is shown to be the atomic hydrogen ionization complicated by its diffusion in the solid phase. The parameters of hydrogen permeability for the systems under study are calculated. The maximum hydrogen permeability is achieved on the Ag80Pd alloy. Accordingly, alloys with higher palladium content, along with pure palladium, can be successfully used as effective materials for the atomic hydrogen purification and storage.