A variety of relative and absolute techniques have been used to measure the reactivity of fluorine atoms with a series of halogenated organic compounds and CO. The following rate constants were derived, in units of cm³ molecule⁻¹ s⁻¹: CH₃F, (3.7 ± 0.8) × 10⁻¹¹, CH₃Cl, (3.3 ± 0.7) × 10⁻¹¹; CH₃Br, (3.0 ± 0.7) × 10⁻¹¹; CF₂H₂, (4.3 ± 0.9) × 10⁻¹²; CO, (5.5 ± 1.0) × 10⁻¹³ (in 700 torr total pressure of N₂ diluent); CF₃H, (1.4 ± 0.4) × 10⁻¹³; CF₃CCl₂H (HCFC‐123), (1.2 ± 0.4) × 10⁻¹²; CF₃CFH₂ (HFC‐134a), (1.3 ± 0.3) × 10⁻¹², CHF₂CHF₂ (HFC‐134), (1.0 ± 0.3) × 10⁻¹²; CF₂ClCH₃ (HCFC‐42b), (3.9 ± 0.9) × 10⁻¹², CF₂HCH₃ (HFC‐152a), (1.7 ± 0.4) × 10⁻¹¹; and CF₃CF₂H (HFC‐125), (3.5 ± 0.8) × 10⁻¹³. Quoted errors are statistical uncertainties (2σ). For rate constants derived using relative rate techniques, an additional uncertainty has been added to account for potential systematic errors in the reference rate constants used. Experiments were performed at 295 ± 2 K. Results are discussed with respect to the previous literature data and to the interpretation of laboratory studies of the atmospheric chemistry of HCFCs and HFCs. © 1993 John Wiley & Sons, Inc.