The rate constants for the two channels of the reaction of F atoms with HD, k F+HD and k F+DH , have been determined in the temperature range 193–300 K. The sum of rate constants k F+HD +k F+DH was determined by a competitive method and a discharge-flow-mass spectrometric technique, using the F+D 2 reaction as a reference reaction. By combining the results for this sum of rate constants with published results for the rate constant kF+D2 and for the ratio of rate constants k F+HD /k F+DH , values were derived for the individual rate constants k F+HD and k F+DH . The experimental results are compared with published results of quantum mechanical calculations and of quasiclassical calculations on the Stark–Werner potential energy surface.