In this study, Pd@TiO2 nanostructure is formed by using TiO2 fibers obtained by the electrospinning method and chemical reduction method, and this nanostructure is used in C2, and C3 alcohol oxidation studies as an application. In addition, TiO2 is compared with the Pd catalyst to investigate the effect of TiO2. In the results obtained, peak current values of 193 and 66.7 mA cm−2 for ethanol oxidation and 127.38 and 36.18 mA cm−2 for 2‐propanol oxidation are observed for Pd@TiO2 and Pd catalysts, respectively. With the addition of TiO2 to the structure, the electrocatalytic activity of C2 and C3 alcohol oxidations increases 3–3.5 times and contributes to the onset potential at an earlier potential. It also shows higher durability and stability in long‐term tests. Moreover, the addition of TiO2 to the structure enhances the electrocatalytic activity and provides high current density and long‐term stability in alcohol oxidation. These results show that fibrous structures in combination with metals improve the effect of catalysts and exhibit high potential for their application in alcohol fuel cells.