A novel approach to synthesis of PtM/C nanoparticulate catalysts based on thermolysis of heterometallic Pt complexes is proposed. Several new heterometallic platinum (II)-based acetate complexes (clusters) with divalent transition metals Pt-II(OOCMe)(4)M-II(OH2) (M = Co, Mn, Zn, Ni) were synthesized and structurally characterized with X-ray crystallography, IR and NMR spectroscopies. The synthesized clusters were used as precursors of bimetallic supported phase for the fuel cell oxygen reduction reaction. After thermal decomposition of the clusters deposited on carbon black, intermetallics with a Pt: M approximate to 1:1 ratio were formed. Physico-chemical and electrochemical characteristics of the prepared bimetallic catalysts PtCo/C, PtMn/C PtZn/C and PtNi/C have been investigated. The bimetallic nano-particles are uniformly distributed over the carbon carrier surface, and grain size in the catalysts is 2-5 nm. The PtZn/C, PtCo/C, PtMn/C and PtNi/C catalysts synthesized from the bimetallic clusters of corresponding metals show advantages over a commercial Pt/C catalyst in the oxygen reduction reaction, PtZn/C in particular, and are promising for use in hydrogen-air fuel cells. (C) 2019 Elsevier Ltd. All rights reserved.