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Reactions of Cl atoms with 3-buten-1-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-1-ol and 4-penten-2-ol were investigated using relative technique with gas chromatograph coupled with flame ionization detection (GC-FID). At 298 ± 1 K and 1.01 × 10⁵ Pa, the rate coefficients measured (in units of 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹) were 3.63 ± 0.49, 4.13 ± 0.56, 3.51 ± 0.48, and 3.62 ± 0.49, respectively. The quoted errors included 2σ from the least-squares analysis and also 10% errors caused by the uncertainty of the reference rate coefficients. In addition, rate coefficients for reactions of the unsaturated alcohols with O₃ were determined using absolute method. The values obtained have been presented, compared with those of their alkene structural homologues and discussed. Reactivity trends and atmospheric implications have also been discussed.