RuO2 is an unparalleled electrode with wider applications. Chloride, bound water, and surface stoichiometry are the inherent residues of RuO2 left upon the high-temperature pyrolysis of a RuCl3⋅xH2O precursor. Although the electrocatalytic properties of RuO2 for specific applications have been studied extensively, there is a paucity of studies linking the intrinsic electron-transfer (ET) activity of RuO2 with the oxide preparation temperature-dependent inherent residual parameters. This paper presents the intrinsic ET activity-oxide residue correlations for RuO2 electrodes. The ET kinetic parameters were estimated using a surface oxide-sensitive Fe3+/Fe2+ redox probe by rotating disc electrode voltammetry. Oxide powder-based electrodes (RuO2 powder-PVC/Pt-modified electrodes), which were fabricated conveniently at room temperature even with high-temperature oxides, were used instead of the traditional thermally prepared electrodes to circumvent the primary problems at the coating|support interface and inefficient chloride removal. RuO2 powders prepared at five temperatures (Tprep), i.e., 300, 400, 500, 600, and 700 °C, were used for electrode fabrication. The results showed that the electron exchange rate was highest for the 400 °C RuO2 electrode, and it was independent of the Tprep in the range 500 to 700 °C. The oxide powders were characterized using a range of techniques. The measured intrinsic ET activity and the associated structural correlation over the Tprep range 300–700 °C suggest that the best activity of the 400 °C electrode can be attributed to the optimal chloride and bound water contents in a completely formed rutile surface layer containing the catalyst sites of a particular nature with the highest electroactivity.