The addition reaction of potassium atoms with oxygen has been studied using the collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) method. KCl vapor was photolyzed with 266 nm pulses and the absorbance by K atoms at 766.5 nm was measured at various delay times with a narrow line width diode laser. Experiments were carried out with O2/N2 mixtures at a total pressure of 1 bar, over 748-1323 K. At the lower temperatures single exponential decays of [K] yielded the third-order rate constant for addition, kR1, whereas at higher temperatures equilibration was observed in the form of double exponential decays of [K], which yielded both kR1 and the equilibrium constant for KO2 formation. kR1 can be summarized as 1.07 × 10(-30)(T/1000 K)(-0.733) cm(6) molecule(-2) s(-1). Combination with literature values leads to a recommended kR1 of 5.5 × 10(-26)T(-1.55) exp(-10/T) cm(6) molecule(-2) s(-1) over 250-1320 K, with an error limit of a factor of 1.5. A van't Hoff analysis constrained to fit the computed ΔS298 yields a K-O2 bond dissociation enthalpy of 184.2 ± 4.0 kJ mol(-1) at 298 K and ΔfH298(KO2) = -95.2 ± 4.1 kJ mol(-1). The corresponding D0 is 181.5 ± 4.0 kJ mol(-1). This value compares well with a CCSD(T) extrapolation to the complete basis set limit, with all electrons correlated, of 177.9 kJ mol(-1).