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Using a relative kinetic technique, rate coefficients have been determined at (298 ± 2) K and atmospheric pressure for the gas‐phase reactions of the NO3 radical with three vicinal dihydroxy aromatic compounds. The experiments were carried out in a 1080‐l quartz glass reactor at the Bergische Universität Wuppertal and in the European Photoreactor (EUPHORE), Valencia, Spain. The rate coefficients obtained (in units of cm3 molecule−1 s−1) using 2,3‐dimethyl‐2‐butene as the reference hydrocarbon were kNO3(1,2‐dihydroxybenzene) = (9.8 ± 5.0) × 10−11, kNO3(1,2‐dihydroxy‐3‐methylbenzene) = (17.2 ± 5.6) × 10−11, and kNO3 (1,2‐ dihydroxy‐4‐methylbenzene) = (14.7 ± 6.5) × 10−11. This study represents the first kinetic investigation of the reactions of the NO3 radical with dihydroxybenzenes. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 577–583, 2004