Abstract The palladium on alumina (Pd@Al 2 O 3 )‐catalyzed hydrogenation of allylbenzene to propylbenzene was studied in methanol and aqueous micellar solutions of sodium dodecyl sulfate (SDS), decyltrimethylammonium bromide (DTAB), and t ‐octylphenoxypolyethoxyethanol (TX‐100). Over Pd@Al 2 O 3 , propylbenzene was obtained via direct hydrogenation of allylbenzene and isomerization to β ‐methylstyrene which was hydrogenated afterwards. In aqueous micellar solutions, the reaction was faster than in pure water, but slower than in methanol due to lower hydrogen solubility. In the H 2 O/SDS system, a higher activation energy was obtained than in methanol. For the investigated surfactants, the initial reaction rate in the micellar systems decreased in the order SDS > TX‐100 > DTAB.