The reaction of dimethylthallium(III) hydroxide with picolinic acid (Hpic), 3-hydroxypicolinic acid (H 2 3hpic) and 6-hydroxypicolinic acid (H 2 6hpic) in an aqueous/methanol mixture afforded the complexes [TlMe 2 (pic)] (1), [TlMe 2 (H3hpic)] (2) and [TlMe 2 (H6hpic)] (3), respectively. Complex 3′, [NaTlMe 2 (6hpic) 2 ] n , was obtained as a minor product from a methanolic solution of 3. Compounds 1–3 were characterized by IR and Raman spectroscopy and, in the cases of 1, 2 and 3′, by single-crystal X-ray diffraction. Complex 3′ is the first example of an H6hpic − heterobimetallic compound to be isolated. The 1 H and 13 C NMR spectra of 1 and 2 are also discussed.