<p>Anti-Markovnikov hydration of unactivated α-alkenes, the direct addition of water to form terminal alcohols, remains a long-standing challenge in catalysis. Previous strategies either are limited on the olefin types, or do not use water directly as the source of oxygen and hydrogen. Here we present a paired electrocatalytic strategy that harnesses water splitting to achieve formal anti-Markovnikov hydration of alkenes in a divided cell. An iron catalyst generates a high-valent metal–oxo species anodically from water to epoxidize the olefin, while a manganese catalyst forms a metal–hydride cathodically that selectively hydrogenates the epoxide via Lewis acid-assisted Meinwald rearrangement, delivering primary alcohols. This membrane-separated process uses water as the oxygen and hydrogen source and electricity as the energy input, enabling the transformation of a broad range of alkyl- and aryl-substituted olefins, including previously inaccessible unactivated α-olefins, into anti-Markovnikov alcohols with high regioselectivity, excellent functional group tolerance and tunable chemoselectivity. Overall, this work showcases a sustainable route to anti-Markovnikov alcohols and provides a conceptual blueprint for leveraging paired electrolysis to drive thermodynamically disfavored reactions.</p>