The bimolecular reaction of ground state cyano radical with propylene under the condition of single collision is investigated by combining ab initio electronic structure calculations for predicting reaction paths and RRKM theory to yield rate constant for each path, The isomerization and dissociation channels for each of the seven collision complexes are characterized by utilizing the unrestricted B3LYP/cc-pVTZ level of theory and the CCSD(T)/cc-pVTZ calculations. Sifting with the facilitation of RRKM rate constants through web of ab initio paths composed of 8 collision complexes, 37 intermediates, and 12 H-, 23 H-2-, 3 HCN-, and 4 CH3-dissociated products, we identify the most probable paths down to 7-9 species at collisions energies of 0 and 5 kcal/mol as the reaction mechanisms. The rate equations of the reaction mechanisms are solved numerically such that the concentration evolutions for all species involved are obtained. This study predicts that CN + C2H3CH3 reaction via any of the seven collision complex, c1-c5, c7, and c8, would produce p1(CH3CHCHCN) + H, p2(CH2CHCH2CN) + H, and mostly p43(vinyl cyanide) + CH3 for collision energy within 0-5 kcal/mol. In addition to the insertion mechanism through collision complex, the direct H-abstraction of propylene by CN radical might occur. Our investigation indicates that the barrierless and exoergic CN(X-2 Sigma(+)) + C2H3CH3(X(1)A') reaction would be an efficient route for the p1, p2, and p43, and likely HCN formation in cold molecular clouds and in the atmosphere of Saturn's satellite Titan.