In our quest to delineate interactions of chromium(III) with ligands often involved in chemistries of toxic and biologically significant manifestations, we have looked into the aqueous structural speciation of the binary system of Cr(III)-heida (2-hydroxyethyliminodiacetic acid). Synthesis in aqueous media led to the isolation of three new species. The complexes were characterized by elemental analysis, spectroscopic, structural, thermal, EPR and magnetic susceptibility studies. The physicochemical properties of the new species project the fundamental features of the interaction of Cr(III) with (O,N)-containing biosubstrates potentially involved in toxic effects manifested at the cellular level.