Using a relative rate method, rate constants have been measured for the gas-phase reactions of the NO₃ radical with methacrolein, a series of ethers, glycol ethers, alcohols and chloroalkenes at 298 ± 2 K and atmospheric pressure of air. The rate constants determined (in units of 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹) were: methacrolein, 33 ± 10; diethyl ether, 31 ± 10; di-n-propyl ether, 49 ± 16; diisopropyl ether, 40 ± 13; ethyl tert-butyl ether, 45 ± 14; 1-methoxypropan-2-ol, ⩽15 ± 5; 2-butoxyethanol, ⩽31 ± 11; propan-1-ol, ⩽21 ± 8; propan-2-ol, ⩽17 ± 6; butan-1-ol, ⩽27 ± 10; butan-2-ol, ⩽25 ± 8; heptan-4-ol, ⩽60 ± 20; cis-1,2-dichloroethene, 1.3 ± 1.3; 1,1-dichloroethene, 18_-6⁺⁹; trichloroethene, 3.6_-1.5^+2.0; tetrachloroethene, <1.8; and 3-chloropropene, 5.8_-2.0^+3.0. Carbonyl products of the alcohol reactions arising after H-atom abstraction at the carbon atom to which the –OH group is attached were observed, and rate constants for this reaction pathway obtained. Significant discrepancies with the literature concern propan-2-ol, ethyl tert-butyl ether and 3-chloropropene, with our relative rate constants for these compounds being factors of ca. 2, ca. 2, and ca. 8 lower, respectively, than previously reported absolute rate constant determinations.