Utilizing the technique of pulsed laser photolysis/pulsed laser induced fluorescence, we have investigated the atmospherically important reactions of the (trifluoromethyl)peroxy radical, CF3O, with several alkanes. The reaction rate coefficients for CF3O + CH4 (k(3)), C2H6 (k4), C3H8 (k(5)), (CH3)(3)CH (k(6)), and CD4 (k(7)) Were measured, as functions of temperature, to be k(3) = (1.92 +/- 0.33) X 10(-12) exp[-(1370 +/- 85)/T] cm(3) molecule(-1) s(-1), k(4) = (4.84 +/- 1.11) X 10(-12) exp[-(400 +/- 70)/T] cm(3) molecule(-1) s(-1), k(5) = (5.12 +/- 1.12) X 10(-12) exp[-(15 +/- 30)/T] cm(3) molecule(-1) s(-1), k(6) = (4.32 +/- 0.42) X 10(-12) exp[(135 +/- 30)/T] cm(3) molecule(-1) s(-1), and k(7) = (0.91 +/- 0.31) X 10(-12) exp[-(1540 +/- 100)] cm(3) molecule(-1) s(-1), respectively. These kinetic data are compared with results from previous studies. The atmospheric implications of these findings are discussed.