Picolinic acid (PA), a C2-carboxylated pyridine derivative, is a significant intermediate used in industrial production. PA is considered hazardous for the environment and human health. In this study, a Gram-positive bacterium, Rhodococcus sp. PA18, which aerobically utilizes PA as a source of carbon and energy, was isolated. The strain completely degraded 100 mg/L PA within 24 h after induction and formed 6-hydroxypicolinic acid (6HPA), a major PA metabolite, which was identified using ultraviolet-visible spectroscopy, high performance liquid chromatography, and liquid chromatography/time of flight-mass spectrometry analyses. The cell-free extracts converted the PA into 6HPA when phenazine methosulfate was used as an electron acceptor. To our knowledge, this is the first report showing that PA can be metabolized by Rhodococcus. In conclusion, Rhodococcus sp. PA18 may be potentially used for the bioremediation of environments polluted with PA.