The reaction of a series of oxygenated aromatics (two methoxybenzene and six methoxyphenol isomers) with chlorine atoms has been studied in two simulation chambers with volumes of 1080 and 480 L at the University of Wuppertal. Experiments were performed at 295 +/- 2 K and a total pressure of synthetic air of 1 bar using the relative kinetic method with in situ Fourier transform infrared spectroscopy for chemical analysis. The following rate coefficients (in units of cubic centimeter per molecule per second) were determined: (1.07 +/- 0.24) x 10(-10) for methoxybenzene, (1.20 +/- 0.24) x 10(-10) for 1-methoxy-2-methylbenzene, (2.97 +/- 0.66) x 10(-10) for 2-methoxyphenol (guaiacol), (2.99 +/- 0.62) x 10(-10) for 3-methoxyphenol, (2.86 +/- 0.58) x 10(-10) for 4-methoxyphenol, (3.35 +/- 0.68) x 10(-10) for 2-methoxy-4-methylphenol, (4.73 +/- 1.06) x 10(-10) for 2,3-dimethoxyphenol, and (2.71 +/- 0.61) x 10(-10) for 2,6-dimethoxyphenol (syringol). To the best of our knowledge, this work represents the first determination of the rate coefficients for the gas-phase reaction of the chlorine atoms with the methoxy-aromatic compounds investigated. The reactivity of the methoxylated aromatics toward Cl is compared with that of other substituted aromatic compounds, and the differences in the rate coefficients are interpreted in terms of the type, number, and position of the different substituents on the aromatic ring. The atmospheric implications of the studied reactions are also discussed.