Several new trinuclear ruthenium carbonyl complexes chelated with 6-bromopyridine alcohol ligands, [6-bromopyC(CH₂)₄O]Ru₃(CO)₉ (1a), [6-bromopyC(CH₂)₅O]Ru₃(CO)₉ (1b), [6-bromopyC(Me)₂O]Ru₃(CO)₉ (1c) and [6-bromopyCMeC₆H₅O]Ru₃(CO)₉ (1d), were synthesized by the reaction of Ru₃(CO)₁₂ with 6-bromopyC(CH₂)₄OH (L¹H), 6-bromopyC(CH₂)₅OH (L²H), 6-bromopyC(Me)₂OH (L³H) and 6-bromopyCMeC₆H₅OH (L⁴H) in refluxing THF, respectively. The free ligands L¹H–L⁴H were synthesized by the nucleophilic reaction of lithium salt (generated from 2,6-dibromopyridine and n-BuLi) with the corresponding ketones. Furthermore, these pyridine-based ligands were characterized by NMR spectroscopy and elemental analyses. All the four ruthenium carbonyl complexes were well characterized by NMR, IR, single-crystal X-ray crystallography, etc. Complexes 1a–1d were found to exhibit high catalytic activities for the dehydrogenative oxidation of secondary alcohols to give their corresponding products in good to excellent yields.