The Precambrian history of our planet is marked by two major events: a pulse of continental crust formation at the end of the Archaean eon and a weak oxygenation of the atmosphere (the Great Oxidation Event) that followed, at 2.45 billion years ago. This oxygenation has been linked to the emergence of oxygenic cyanobacteria(1,2) and to changes in the compositions of volcanic gases(3,4), but not to the composition of erupting lavas-geochemical constraints indicate that the oxidation state of basalts and their mantle sources has remained constant since 3.5 billion years ago(5,6). Here we propose that a decrease in the average pressure of volcanic degassing changed the oxidation state of sulphur in volcanic gases, initiating the modern biogeochemical sulphur cycle and triggering atmospheric oxygenation. Using thermodynamic calculations simulating gas-melt equilibria in erupting magmas, we suggest that mostly submarine Archaean volcanoes produced gases with SO(2)/H(2)S < 1 and low sulphur content. Emergence of the continents due to a global decrease in sea level and growth of the continental crust in the late Archaean then led to widespread subaerial volcanism, which in turn yielded gases much richer in sulphur and dominated by SO(2). Dissolution of sulphur in sea water and the onset of sulphate reduction processes could then oxidize the atmosphere.