Stepwise down: Reaction of [Cu(Me2‐tpa)]+ (tpa=bis(6‐methyl‐2‐pyridylmethyl)(2‐pyridylmethyl)amine) with H2O2 results in regioselective oxidation of a methyl group of the Me2‐tpa ligand to produce an alkylperoxocopper(II) complex [Cu(Me‐tpa‐CH2OO)]+ as a reaction intermediate, which undergoes further decomposition to give aldehyde and alcohol copper(I) complexes as well as alkoxo‐ and carboxylatocopper(II) complexes (see scheme; blue N, green Cu, red O).