The electrochemical properties of rhodium(III) 1-3 and iridium(III) 4-6 complexes containing bis(pyrazolyl) alkane ligands [MCp*Cl(R2C(3,5-R' (2)pz)(2))] X (M = Rh (1) or Ir (4), R = R' = H, X = Cl; M = Rh (2) or Ir (5), R = H, R' = Me, X = Cl; M = Rh (3) or Ir (6), R = Me, R' = H, X = OTf; pz = pyrazolyl; Cp* = eta(5)-C5Me5) were investigated by cyclic voltammetry and controlled potential electrolysis. They exhibit two sequential irreversible reductions assigned to the M-III -> M-II and M-II -> M-I reductions, which are dependent on the methylation of the bis(pyrazolyl) alkane ligands.