The major alkaloids of three species of Polhillia Stirton and three species of Argyrolobium Eckl. & Zeyh. have been identified. The presence of sparteine, lupanine, anagyrine and N-methylcytisine as major alkaloids in Polhillia and in the morphologically similar Argyrolobium brevicalyx Stirton indicates a direct phylogenetic link between Polhillia (Crotalarieae) and Argyrolobium (Genisteae). The data also supports the transfer of Melolobium involucratum (Thunb.) Stirton to Polhillia.