The tungsten-modified titanium dioxide, which prepared through the one-pot solvothermal process, exhibited the large specific surface area (~ 202 m2/g) and greater electrical conductivity (~ 0.022 S/cm). Furthermore, for the comparison purpose to find appropriate approach for the synthesis 20 wt. % Pt NPs/Ti0.7W0.3O2 catalyst, the modified chemical reduction utilizing NaBH4 and the rapid microwave-assisted polyol using ethylene glycol were employed without any surfactants or stabilizers. The characterization of Pt-based electrocatalyst was investigated through XRD, SEM-EDX, TEM measurements. As result, the platinum nanocatalyst formation with the face-centered cubic structure (fcc) and the amount loading on Ti0.7W0.3O2 support approximately 20 wt. % of two synthesized methods. However, the diameter size and distribution of Pt nanoforms have clearly classified in two reduction route. For example, the Pt nanocatalyst, which was created by the rapid microwave-assisted polyol at 160 °C for 2 min, exhibited the good distribution on support with ~3 nm diameter. This could be ascribed to the fast and uniform heating of microwave-assisted and moderate reducing possibility of ethylene glycol. These results indicate that the rapid microwave-assisted polyol was an appropriate approach not only for synthesizing 20 wt. % Pt NPs/Ti0.7W0.3O2 catalyst but also for preparing Pt-based electrocatalysts.