Degradation of the catalyst and catalyst support is an essential limitation of polymer electrolyte membrane (PEM) fuel cells containing commercial platinum on carbon catalysts. Catalysts based on platinum nanoparticles coated onto nanostructured TiO2 materials are presently investigated as a more stable and equally cost effective alternative. Reported here is the synthesis of two different Pt/Nb0.1Ti0.9O2 catalysts that were prepared by chemical reduction of H2PtCl6 with either sodium borohydride in ethanolic surfactant solution or ethylene glycol. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and high-resolution transmission electron microscopy confirmed the deposition of Pt nanoparticles on the surface of the nanofibers and revealed average sizes of 5.4 nm and 7.6 nm for reduction with ethylene glycol and sodium borohydride, respectively. The formation of smaller sized Pt nanoparticles in ethylene glycol is reasoned with the passivation of the nanoparticle surface by glycolic anions. Cyclic voltammetry measurements confirmed a higher electrochemical specific surface area (ESCA) of about 5.45 m2/gPt for the catalyst with smaller nanoparticles while the other catalyst reached only 4.96m2/gPt. Both catalysts retain about 60% of their electrochemically active surface area after 1000 voltammetric cycles in the range of 0.03 to 1.4 V vs. RHE. This relatively high value of activity retention is explained with a strong interaction between Pt nanoparticles and Nb0.1Ti0.9O2 support.