Phosphoglucose isomerase (PGI, EC 5.3.1.9) isozymes were examined by electrophoresis in the three common British species of Polygala, the diploids P. serpyllifolia and P. calcarea and the tetraploid P. vulgaris. All three species share the most anodal band which is probably the form of the enzyme occurring in the plastids (PGI-1). Individuals of the two diploid species each have one further band, probably the cytosolic form of the enzyme (PGI-2), with two phenotypes in each species, one of which is common to both. Individuals of P. vulgaris have one, three or six PGI-2 bands and 10 different homozygous phenotypes were observed. The commonest phenotypes in most populations show three bands with a central heterodimeric band staining more intensely than the outer two bands. Although P. vulgaris is a predominantly seif-fertilising species with no vegetative spread, many populations or sub-populations consist almost entirely of three-banded phenotypes. This indicates that the three-banded phenotypes are "fixed heterozygotes" resulting from the duplication of the Pgi-2 locus in the tetraploid. Heterozygotes between different three-banded forms show six bands in which the staining intensities are consistent with random pairing of the subunits. Plants showing silencing of one of the duplicate alleles were found in two small isolated areas in West Glamorgan. The biochemical diversity produced by the multiplicity of enzyme morphs in the tetraploid P. vulgaris may have contributed to its success. It is the most common, widespread and ecologically wide-ranging species in the genus in Europe.