Nature Catalysis, Published online: 14 August 2026; doi:10.1038/s41929-026-01595-8 Methanol electrooxidation on Pt is believed to follow parallel indirect and direct mechanisms, involving CO* or OOCH intermediates, respectively. Now operando electrochemical mass spectrometry and theoretical calculations are used to propose an alternative, more prevalent mechanism in which C–O bond cleavage occurs.