Gallium(III) compounds were first shown to have anticancer properties in 1971 and there has been much research into developing gallium(III) into a new weapon against cancer, utilizing both radioactive (67Ga ?, t1/2 = 3.25 d, 68Ga ?+, t1/2 = 68 min) and non-radioactive isotopes [2]. Oral ingestion of gallium compounds has been shown to be less toxic than parenteral administration in humans and work has therefore focused primarily on producing gallium complexes with oral bioavailability. Humans have an active transport mechanism for the absorption and cellular uptake of certain vitamin molecules. Vitamins such as folic acid (B9), thiamin (B1) or cobalamin (B12) have the potential to act as drug delivery vectors if an active pharmaceutical can be tethered to them. In addition to increasing oral absorption and transport into blood serum and across the cell membrane, these vitamins should also protect the drug from extraneous reactions with proteins and metabolites present in all biological fluids. As part of our efforts to synthesize gallium bioconjugates based on folic acid and thiamin we have utilized 1,4,7,10-tetraazacyclo-dodecane-N,N?,N??,N???-tetraacetic acid (DOTA) as the chelating ligand for gallium(III). The reaction of gallium chloride with DOTA at room temperature in aqueous solution affords the complex [Ga(HDOTA)·5.5H2O], 1, which is characterized by single-crystal X-ray spectroscopy, electrospray mass spectrometry and thermal gravimetric analysis. Gallium displays 6-coordinate distorted octahedral geometry within a puckered macrocyclic DOTA framework.