Barley grains mutagenized with sodium azide were screened for high levels of free phosphate in order to identify low‐phytate mutants. Approximately 2000 M2 half‐grains were analyzed by molybdate staining and high free phosphate contents were scored positive for low phytate mutants. Plants were grown from embryo‐containing halves of positive samples. Subsequent TLC analysis of positives was used to display free phosphate and phytate simultaneously, and two characteristic low‐phytic acid phenotypes (A and B) could be distinguished. A‐type grains, which were found for seven plants, contained very high levels of free phosphate, low levels of phytate and trace amounts of other phosphate‐containing compounds not observed in wildtype samples. Migration of these novel P‐compounds on TLC plates was similar to that of inositol phosphates other than phytate. In grains from the two B‐type plants the increase in free phosphate and the decrease in phytate relative to wildtype levels were moderate and additional P‐compounds were absent. Genetic tests showed that at least three recessive alleles caused low‐phytic acid phenotype A, whereas a separate, recessive locus was responsible for phenotype B. The importance of these findings with respect to the development of new barley varieties with an improved nutritional and environmental value is discussed.