The reactions of Cl atoms with 2,3-butadione (k₁), 2-butanone (k₂), 2-pentanone (k₃), 2-hexanone (k₄), 3-methyl-2-butanone (k₅), 4-methyl-2-pentanone (k₆) and 5-methyl-2-hexanone (k₇), were investigated for the first time as a function of temperature (266–380 K), over the pressure range 20–200 Torr, using pulsed laser photolysis-resonance fluorescence (PLP-RF). The Arrhenius expressions for the seven reactions are proposed. The temperature dependence of the studied reactions is discussed; the reaction of Cl atoms with 2,3-butadione exhibits a positive temperature dependence whereas the corresponding reactions with 2-pentanone, 2-hexanone, 4-methyl-2-pentanone and 5-methyl-2-hexanone exhibit a negative temperature dependence and those with 2-butanone and 3-methyl-2-butanone shows only a slightly positive and a negative temperature dependence, respectively. Finally, the results and atmospheric implications are discussed and compared with the reactivity towards the OH radical.