A newly constructed chamber/Fourier transform infrared system was used to determine the relative rate coefficient, ki, for the gas-phase reaction of Cl atoms with 2-butanol (k1), 2-methyl-2-butanol (k2), 3-methyl-2-butanol (k3), 2,3-dimethyl-2-butanol (k4) and 2-pentanol (k5). Experiments were performed at (298 ± 2) K, in 740 Torr total pressure of synthetic air, and the measured rate coefficients were, in cm3 molecule−1 s−1 units (±2σ): k1
=
(1.32 ± 0.14)
× 10−10, k2
=
(7.0 ± 2.2)
× 10−11, k3
=
(1.17 ± 0.14)
× 10−10, k4
=
(1.03 ± 0.17)
× 10−10 and k5
=
(2.18 ± 0.36)
× 10−10, respectively. Also, all the above rate coefficients (except for 2-pentanol) were investigated as a function of temperature (267–384 K) by pulsed laser photolysis–resonance fluorescence (PLP-RF). The obtained kinetic data were used to derive the Arrhenius expressions: k1(T)
=
(6.16 ± 0.58)
× 10−11exp[(174 ± 58)/T], k2(T)
=
(2.48 ± 0.17)
× 10−11exp[(328 ± 42)/T], k3(T)
=
(6.29 ± 0.57)
× 10−11exp[(192 ± 56)/T], and k4(T)
=
(4.80 ± 0.43)
× 10−11exp[(221 ± 56)/T]
(in units of cm3 molecule−1 s−1 and ±σ). Results and mechanism are discussed and compared with the reported reactivity with OH radicals. Some atmospheric implications derived from this study are also reported.