Two polyaminothiol ligands, one hexadentate, N,N',N"-tris[2-methyl(2-propanethiol)]-1,4,7-triazacyclononane (TACN), and another potentially heptadentate, tris[2-methyl(2-propanethiol)]aminoethylamine (TMAE), were synthesized and characterized using spectroscopic and analytical methods. Both ligands were labeled with gallium-67 at pH 3.0-3.5 in high yields. The resulting gallium chelates were lipophilic. The biodistribution studies for both the chelates showed hepatic uptake and biliary clearance. The total % ID activity for [67Ga]TACN in liver and intestine at 5 min was 33.86 increasing gradually to 61.4% at 30 min. The chelates were in vivo stable to plasma-transferrin transchelation as confirmed by scintigraphic images obtained by [67Ga]TACN in rats and by plasma incubation of the chelates. These results indicate that Ga-TACN is a potentially useful tracer for hepatobiliary imaging using PET. No brain uptake was found.