The gas-phase reactivity of ground-state Re(a(6)S(5/2)) with O-2, NO, N2O, and CH4 is reported. Rhenium atoms were produced by the photodissociation of Re(CO)(5)Cl and detected by laser-induced fluorescence. The reaction rate of the a(6)S(5/2) state with O-2 is slow and temperature-dependent. The reaction is pressure-independent, indicating a bimolecular abstraction reaction. The bimolecular rate constant from 296 to 548 K is described in Arrhenius form by (2.1 +/- 0.3) x 10(-11) exp(-11.6 +/- 0.6 kJ/mol/RT) where the uncertainties represent +/- 2 sigma. The reaction rate of the a(6)S(5/2) state-with NO is pressure-dependent, indicating adduct formation. The limiting low-pressure third-order, k(0), and limiting high-pressure second-order, k(infinity), room-temperature rate constants with NO in nitrogen buffer are (3.7 +/- 0.8) x 10(-30) cm(6) s(-1) and (7.0 +/- 0.8) x 10(-12) cm(3) s(-1), respectively. There is no evidence of chemical reaction for the ground state of rhenium with N2O or CH4 up to a temperature of 548 K.