Phase relations in the binary system K2O‐GeO2 were determined by conventional quenching techniques. Three compounds, K2O.2GeO2, 3K2O.11GeO2, and K2O.7GeO2, exist in the composition range 65 to 100% GeOn. The compound 3K2O.1lGeO2 melts congruently at 1055°C, whereas K2O.2GeO2 and K2O.7GeO2 melt incongruently at 761° and 950°C, respectively. Thermal expansion data for the crystalline compounds are presented. The structure of potassium germanate glasses is discussed. Copyright © 1968, Wiley Blackwell. All rights reserved