Absolute rate constants for reactive removal and vibrational relaxation have been determined for the collisions of OH(X(2)Pi(i), v = 1 and 2) with CH4. The hydroxyl radical was produced in the reaction O(D-1) + CH4 --> OH(X(2)Pi(i), v less than or equal to 4) + CH3 initiated by the 248 nm photolysis of O-3 in the presence of CH4. All the vibrational levels of OH(v) were detected by laser-induced fluorescence (LIF) via the sequences Delta v = O (v" = 0, 1, and 2) and Delta v = -3 (v" = 3 and 4) of the A(2)Sigma(+)-X(2)Pi(i) transition. Temporal profiles of the LIF intensities were analyzed using a new linear regression method (refs 10 and 11), and total removal rate constants for the vibrational levels (v = 1-4) were determined. The linear analysis coupled with the previously reported nascent vibrational distributions of OH gave absolute rate constants for the reactive and nonreactive removal of OH(v). Rate constants for reactive removal, OH(v) + CH4 --> products, were determined to be k(v=1) = (2.1 +/- 0.6) x 10(-13) cm(3) molecule(-1) s(-1) and k(v=2) = (0.9 +/- 0.4) x 10(-12) cm(3) molecule(-1) s(-1), and for vibrational relaxation, OH(v) + CH4 --> OH(v - 1) + CH4, are k(1-->0) = (3.5 +/- 0.6) x 10(-13) cm(3) molecule(-1) s(-1) and k(2-->1) = (1.1 +/- 0.4) x 10(-12) cm(3) molecule(-1) s(-1). This article is the first report on the branching ratios between reactive removal and vibrational relaxation.