This paper describes a study of reactivity and enantioselectivity for a series of methyl-substituted styrenes in the Jacobsen - Katsuki (Mn(salen)-catalyzed) epoxidation reaction. Competition experiments provided kinetic data for the reactivity of the seven possible methyl-substituted styrenes (mono-, di- and trisubstituted) relative to styrene itself, ee values were measured by chiral GC, and absolute configurations were secured by chemical correlation. Of particular interest was the switch in absolute configuration at the benzylic position of the epoxides derived from (Z)- and (E)-alpha,beta-dimethylstyrene, respectively. The results could be rationalized in terms of an approach vector with the phenyl substituent proximal to the salen. As opposed to alkyl groups, a proximal phenyl group has very little effect on the rate of the reaction. Consideration of distal vs proximal approach allows prediction of absolute stereochemistry as a function of alkene substitution pattern. Trisubstituted alkenes with one phenyl group cis to the alkene hydrogen can be identified as a favored substrate class in the title reaction, with both rate and selectivity close to the classic (Z)-beta-substituted styrene substrates.