The rate constants for the reaction of the OH radical with 1,3-butadiene and its deuterated isotopomer has been measured at 1-6 Torr total pressure over the temperature range of 263-423 K using the discharge flow system coupled with resonance fluorescence/laser-induced fluorescence detection of OH. The measured rate constants for the OH + 1,3-butadiene and OH + 1,3-butadiene-d(6) reactions at room temperature were found to be (6.98 0.28) x 10(-11) and (6.94 0.38) x 10(-11) cm(3) molecule(-1) s(-1), respectively, in good agreement with previous measurements at higher pressures. An Arrhenius expression for this reaction was determined to be k(1)(II) (T) = (7.23 +/- 1.2) x 10(-11) exp [(664 +/- 49)/T] cm(3) molecule(-1) s(-1) at 263-423 K. The reaction was found to be independent of pressure between 1 and 6 Torr and over the temperature range of 262- 423 K, in contrast to previous results for the OH + isoprene reaction under similar conditions. To help interpret these results, ab initio molecular dynamics results are presented where the intramolecular energy redistribution is analyzed for the product adducts formed in the OH + isoprene and OH + butadiene reactions.