Rate constants as a function of temperature for the reaction Al + SF6 have been measured under pseudo-first-order conditions. Laser-induced fluorescence was used to monitor the relative concentrations of either the reactant Al or the primary product AlF. The measured rate constants are described by the expression k(T) = 6.8 (+/-2.2) x 10(-10) exp(-(4780 +/- 200 K)/T) cm(3) molecule(-1) s(-1) over the range 499-813 K. Ab initio and density functional calculations at the MP2(FC) and BH&HLYP levels have been used to model the potential energy surface for this reaction. Calculated rate constants are in good agreement with experimental 9 observations.