Volcanic rocks in Archean and Paleoproterozoic greenstone belts are abundant and have been suggested as a potential Au source for orogenic Au deposits. The behavior of Au during metamorphism of these rocks is, however, poorly known. We present ultra-low-detection-limit Au analyses from a suite of variably metamorphosed rocks from the Archean La Grande subprovince, Canada, and the Paleoproterozoic Central Lapland greenstone belt, Finland. Both areas are well endowed in Au and have great potential for discovery of new orogenic Au deposits. The metavolcanic rocks in these belts are grouped into tholeiite and calc-alkaline magmatic series, for which the protolith Au contents are calculated using Au versus Zr/Y power-law regressions from greenschist facies samples. In the tholeiitic rocks, Au is compatible during magmatic processes and decreases with differentiation, whereas in the calc-alkaline rocks, Au is incompatible and increases with differentiation. Mass-variation calculations show that as much as 77% and 59% of the initial Au content is lost during progressive metamorphism to upper amphibolite facies conditions (>550 °C) in La Grande and Central Lapland respectively. This study highlights, first, that metavolcanic rocks release Au during metamorphism in Archean and Paleoproterozoic greenstone belts and are thus a good potential source rocks for orogenic Au deposits; second, that the Au fertility of the metavolcanic rocks is controlled by their mantle source and magmatic evolution; and third, that the metamorphic devolatilization model can be applied to Archean and Paleoproterozoic orogenic Au deposits.