Platinum electrocatalysts were prepared using PtCl4 as a starting material and 1-decylamine, N,N-dimethyldecylamine, 1-dodecylamine, N,N-dimethyldodecylamine, 1-hexadecylamine, and 1-octadecylamine as surfactants. These surfactants were used for the first time in this synthesis to determine whether the primary and/or tertiary structure and/or chain length of the surfactants, affects the size and/or activity of the catalysts in C1–C3 alcohol electro-oxidation reactions. Electrochemical measurements (cyclic voltammetry and chronoamperometry) indicated that the highest electrocatalytic performance was observed for the Pt nanocatalysts that were stabilized by N,N-dimethyldecylamine, and this has a tertiary amine structure with a short chain length (R = C10H21). The high performance may be due to the high electrochemical surface area, Pt(0)/Pt(IV) ratio, %Pt utility, and roughness factor (Rf). X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy, and transmission electron microscopy were used to determine the parameters that affect the catalytic activities.