The mechanism of CH(X-2 Pi) reaction with propene has been studied with ab initio CCSD(T)-F12/CBS//B3LYP/6-311G(d,p) calculations of the C4H7 potential energy surface and RRKM/master equation calculations of unimolecular rate constants for the various isomerization and dissociation steps available to the C4H7 radicals. Product branching ratios were calculated and were found to strongly depend on the initial chemically activated C4H7 complex formed in a barrierless entrance channel. If the reaction is initiated via either CH addition to the double bond in propene or CH insertions into the terminal sp(2) C-H or single C-C bonds, then 1,3-butadiene + H are predicted to be the dominant products, ethene + C2H3 radical are minor but non-negligible products, and a small amount of 1,2-butadiene + H is also produced. The reaction then proceeds through a key (CH3CHCHCH2)-C-center dot intermediate, which loses an H atom to form either 1,3- or 1,2-butadiene or isomerizes to (CH2CH2CHCH2)-C-center dot and then dissociates to ethene + C2H3 radical. If CH inserts into a C-H bond in the CH3 group the (CH2CH2CHCH2)-C-center dot complex is formed directly and then the major reaction products are predicted to be ethene + C2H3 radical and 1,3-butadiene + H. Finally, if CH inserts into the middle sp(2) C-H bond, a branched CH3C((CH2)-C-center dot)CH2 complex is produced, which predominantly decomposes to allene + CH3 radical. A comparison of the calculated reaction mechanism with available experimental data indicates that the CH addition entrance channel is favorable, in which case the computed branching ratios are in agreement with the experimental result of Loison and Bergeat, who measured the H elimination branching ratio of 78 +/- 10%. However, the computed branching ratios quantitatively disagree with the experimental data by Trevitt et al., who observed a nearly 100% yield of the C4H6 + H products and also larger yields of 1,2-butadiene and 1-butyne than the calculations predict. The deviation of the theoretical results from experiment can be rationalized in terms of dynamical factors, which should favor direct dissociation of the (CH3CHCHCH2)-C-center dot precursor by H loss, especially to 1,2-butadiene, over its isomerization to (CH2CH2CHCH2)-C-center dot followed by the production of ethene + C2H3 radical, while 1-butyne might be formed through secondary H assisted isomerization of 1,2-butadiene. Overall, the calculations corroborate that the CH + C3H6 reaction could be a major source of 1,3-butadiene at low temperature and low pressure conditions in the interstellar medium and planetary atmospheres.