The overall rate constants for reactions of O(P-3) with three fluoroethanes, O(P-3)+CH3CH2F->OH + CH2CH2F/CH3CHF (1), O(P-3) + CH2FCH2F -> OH + CHFCH2F (2), and O(P-3) + CH3CHF2 -> OH+ CH2CHF2/ CH3CF2 (3), were measured by laser flash photolysis in shock heated sample gases at 1000-1400 It. The rate constants were obtained in the simple Arrhenius form, k = A exp(-E-a/RT), where A = 2.19 x 10(-9), 1.24 x 10(-9) and 7.43 x 10(-9) cm(3) molecule(-1) s(-1) and E-a = 58.0, 57.0 and 82.7 kJ mol(-1), and uncertainty factors for k at 2 sigma level are F = 1.36, 1.27 and 1.19, respectively, The effect of substitution of the fluorine atom on the overall rate constant is discussed in comparison with the corresponding rates for a series of alkanes and fluoromethanes. (C) 2001 Published by Elsevier Science B.V.