The oxidation state of volcanic gas emissions influences the composition of the exosphere and planetary habitability. It is widely considered to be associated with the oxidation state of the melt from which volatiles exsolve. Here, we present a global synthesis of volcanic gas measurements. We define the mean oxidation state of volcanic gas emissions on Earth today and show that, globally, gas oxidation state, relative to rock buffers, is a strong function of emission temperature, increasing by several orders of magnitude as temperature decreases. The trend is independent of melt composition and geodynamic setting. This observation may explain why the mean oxidation state of volcanic gas emissions on Earth has apparently increased since the Archean, without a corresponding shift in melt oxidation state. We argue that progressive cooling of the mantle and the cessation of komatiite generation should have been accompanied by a substantial increase of the oxidation state of volcanic gases around the onset of the Great Oxidation Event. This may have accelerated or facilitated the transition to an oxygen-rich atmosphere. Overall, our data, along with previous work, show that there is no single nor simple relationships between mantle, magmas and volcanic gas redox states.