Abstract Composition and zoning of amphibole in agpaitic pegmatites of the 1.16 Ga Ilimaussaq complex, South Greenland record the chemical evolution of the final stages of an already extremely fractionated melt. Our results show that the general differentiation trends found in the earlier rocks of the complex are continued in the pegmatites, albeit with some significant modifications: the dominating exchange mechanism of Na + Si ⇔ Ca + Al in the amphiboles of the magmatic stage changes to K + Si ⇔ Ca + Al and K ⇔ Na in some pegmatitic samples. Na/K ratios in amphiboles, which generally increase in the course of the Ilimaussaq fractionation, partly display a reversal during the crystallization of the most differentiated amphiboles. The alkali trends are probably related to the buffering of Na+and K+activity by the co-crystallization of albite and microcline. This buffering favors Na+in cooling fluids. This mechanism is lost when analcime replaces feldspar as a stable phase in the late stages of crystallization, e.g. due to locally elevated H2O activity. Analcime does not incorporate significant amounts of K and accordingly, amphibole incorporates more K in analcime-bearing assemblages. The Na–K variation in amphiboles in the Ilimaussaq pegmatites allow a detailed view into the late-stage evolutionary trends of a textbook agpaitic complex. The transition from silicate melt to aqueous fluid is recorded by the change of the dominant alkali ion in the pegmatitic amphiboles from Na to K. Only in the very latest stage, virtually K-free mineral assemblages in analcime–aegirine veins support the existence of a Na-dominated aqueous fluid.