Gallium maltolate, tris(3‐hydroxy‐2‐methyl‐4H‐pyran‐4‐onato)gallium (GaM), is an orally active gallium compound for therapeutic use. It is moderately soluble in water (10.7 ± 0.9 mg/mL at 25 ∘C) with an octanol partition coefficient of 0.41±0.08. The molecule is electrically neutral in aqueous solution at neutral pH; a dilute aqueous solution (2.5 ×10−5 M) showed little dissociation at pH 5.5‐8.0. Single crystal X‐ray diffraction analysis found the GaM molecule to consist of three maltolate ligands bidentately bound to a central gallium atom in a propeller‐like arrangement, with one of the ligands disordered in two possible orientations. The compound is orthorhombic, space group Pbca, unit cell a = 16.675(3), b = 12.034(2), c = 18.435(2) at 158K. GaM was administered to healthy human volunteers at single doses of 100, 200, 300, and 500 mg (three subjects per dose). GaM was very well tolerated. Oral absorption of Ga into plasma was fairly rapid (absorption half life = 0.8‐2.0h), with a central compartment excretion half life of 17‐21h. Absorption appeared dose proportional over the dosage range studied. Estimated oral gallium bioavailability was approximately 25‐57%, based on comparison with published data on intravenous gallium nitrate. Urinary Ga excretion following oral GaM administration was approximately 2% of the administered dose over 72h, in contrast to 49‐94% urinary Ga excretion over 24h following i.v. gallium nitrate administration. We suggest that oral administration of GaM results in nearly all plasma gallium being bound to transferrin, whereas i.v. administration of gallium nitrate results in formation of considerable plasma gallate [Ga], which is rapidly excreted in the urine. These data support the continued investigation of GaM as an orally active therapeutic gallium compound.