X‐ray photoelectron spectroscopy (XPS), x‐ray diffraction (XRD), and extended x‐ray adsorption fine structure (EXAFS) were used for the characterization of a highly dispersed Ti‐promoted Pt electrocatalyst. This bimetallic catalyst was prepared by addition of , to a methanol‐water solution containing Pt on carbon black catalyst in suspension. Following filtration and air drying (300°C), heat‐treatments up to 1200°C under flowing helium were performed to promote the formation of Pt‐Ti alloy phases. XPS indicated the development of a peak at a binding energy of 454.9 eV (assigned to Ti in), which increased in area with heat‐treatment such that after the 1200°C heat‐treatment ≈50% of the Ti was converted to the intermetallic phase, . The Pt (4f, 7/2) photoelectron line shifted (+0.3 eV) to 71.2 eV following the 1200°C heat‐treatment, identical to the Pt (4f, 7/2) binding energy for bulk . XRD showed only fcc reflections, indicating the excess Ti present as was x‐ray amorphous. Prior to heat‐treatment of the Ti impregnated catalyst, the fcc reflections indicated a lattice parameter of 3.927Å, identical to that for pure Pt. As heat‐treatment temperature increased the lattice parameter decreased to 3.906Å, the value for bulk . Particle size estimates indicated a progressive increase in the crystallite size of Pt alloy phase with temperature to a final size of ≈150Å at 1200°C. Definitive proof of an ordered phase was the presence of superlattice diffraction lines from materials heated above 900°C. EXAFS of these catalysts confirmed the conversion of an initial mixture to at 900°–1200°C heat‐treatment temperatures.