PtPb ordered intermetallic nanoparticles (NPs) were deposited on titanium oxide (TiO2)/cup-stacked carbon nanotubes (CSCNT) to improve the activity of the electrochemical oxygen reduction reaction (ORR). The use of CSCNTs as a support material resulted in high loading of PtPb NPs/TiO2. The PtPb NPs/TiO2/CSCNTs were prepared by the step-by-step preparation method, viz, first annealing under an inert atmosphere with Ti-alkoxide to obtain TiO2, then Pt NP photodeposition, and finally microwave synthesis to prepare ordered intermetallic PtPb NPs on TiO2 via reaction of Pb2+ with Pt/TiO2. The new particles enhanced ORR electrocatalytic activity.