We report the electron transfer (ET) self-exchange rate constants (k11) for a pair of CuII/I complexes utilizing dpaR (dpa = dipicolylaniline, R = OMe, SMe) ligands assessed by NMR line-broadening experiments. These ligands afford copper complexes that are conformationally dynamic in one oxidation state. With R = OMe, the CuI complex is dynamic, while with R= SMe, the CuII complex is dynamic. Both complexes exhibit unexpectedly large k11 of 2.48(6) x 105 and 2.21(9) × 106 M‒1 s‒1 for [CuCl(dpaOMe)]+/0 and [CuCl(dpaSMe)]+/0, respectively. Among the fastest reported for molecular copper coordination complexes to date, that of [CuCl(dpaSMe)]+/0 exceeds all others by an order of magnitude and compares only to those observed in type 1 blue copper proteins. The dynamicity of these complexes establish pre-steady-state con-formational equilibria that minimize the inner sphere reorganization energies to 0.71 and 0.62 eV for R = OMe and SMe, respectively. In contrast to the emphasis on rigidity in the formulation of entatic states applied to blue copper proteins, the success of these two systems highlight the relevance of conformational dynamicity in mediating rapid ET.