The comparative interfacial oxidation kinetics of the approximate structural isomers trans-(O)(2)Re-V(py)(4)(+) and cis(O)(2)Re-V(bpy)(PY)(2)(+) (Py, pyridine; bpy, 2,2’-bipyridine) have been assessed in aqueous solution via conventional cyclic voltammetry at a highly ordered pyrolytic graphite (HOPG) electrode. HOPG was employed because of its known propensity to diminish interfacial electron transfer (ET) rates (by ca. three to four orders of magnitude) and because of a probable lack of importance of kinetic work terms (diffuse double-layer corrections). Measured rates for the trans complex exceed those for the cis by about a factor of 3. Expressed as an effective activation Gibbs energy difference Delta G*, this corresponds to a cis-trans difference of ca. 3 kJ mol(-1). The actual vibrational barriers to ET have determined from a combination of published X-ray structural results (trans complex) and new resonance Raman results (cis complex). The values are 0.6 kJ mol(-1) for the trans oxidation and 4.4 kJ mol(-1) for the cis oxidation (i.e. close to the barrier difference inferred from rate measurements). Further analysis shows that most of the barrier difference is associated with displacement of a (predominantly) Re-N(bpy) stretching mode found only in the cis system. Differences in metal-ore displacements (cis > trans) are also implicated.