We conducted the crossed molecular beams reactions of the phenyl and D5-phenyl radicals with propylene together with its partially deuterated reactants at collision energies of ~45 kJ mol(-1) under single collision conditions. The scattering dynamics were found to be indirect and were mainly dictated by an addition of the phenyl radical to the sterically accessible CH(2) unit of the propylene reactant. The resulting doublet radical isomerized to multiple C(9)H(11) intermediates, which were found to be long-lived, decomposing in competing methyl group loss and atomic hydrogen loss pathways with the methyl group loss leading to styrene (C(6)H(5)C(2)H(3)) and the atomic hydrogen loss forming C(9)H(10) isomers cis/trans 1-phenylpropene (CH(3)CHCHC(6)H(5)) and 3-phenylpropene (C(6)H(5)CH(2)C(2)H(3)). Fractions of the methyl versus hydrogen loss channels of 68 ± 16% : 32 ± 10% were derived experimentally, which agrees nicely with RRKM theory. As the collision energy rises to 200 kJmol(-1), the contribution of the methyl loss channel decreases sharply to typically 25%; the decreased importance of the methyl group loss channel was also demonstrated in previous crossed beam experiments conducted at elevated collision energies of 130-193 kJ mol(-1). The presented work highlights the interesting differences of the branching ratios with rising collision energies in the reaction dynamics of phenyl radicals with unsaturated hydrocarbons related to combustion processes. The facility of forming styrene, a common molecule found in combustion against the elusiveness of forming the cyclic indane molecule demonstrates the need to continue to explore the potential surfaces through the combinative single collision experiment and electronic structure calculations.