To reflect magmatic conditions, volcanic rocks must retain their compositions through eruption and post-eruptive cooling. Mostly, this is the case. However, welded ignimbrites from the Yellowstone-Snake River Plain magmatic province reveal systematic modification of the lithium (Li) inventory by post-eruptive processes. Here we show that phenocrysts from slowly cooled microcrystalline ignimbrite interiors consistently have significantly more Li than their rapidly quenched, glassy, counterparts. The strong association with host lithology and the invariance of other trace elements indicate that Li remains mobile long after eruption and readily passes into phenocrysts via diffusion as groundmass crystallisation increases the Li contents of the last remaining melts. Li isotopic measurements reveal that this diffusion during cooling combined with efficient degassing on the surface may significantly affect the Li inventory and isotopic compositions of volcanic rocks. Utilisation of Li for petrogenetic studies is therefore crucially dependent on the ability to 'see through' such post-eruptive processes.