Hydrogenolysis of alpha-methylbenzyl alcohol (MBA), a co-product of propylene oxide (PO) in hydrocarbon peroxide oxidation processes, was studied to develop a by-product-free PO process. The conversion of MBA was mainly affected by the acidity of the support. Among the metals tested, Pd was most active and selective for the formation of ethylbenzene (EB). The hydrogenation of MBA exhibited type II selectivity, meaning that the selectivity to main products is controlled by reaction conditions and metals chosen. On Pd or Ni, the formation of EB is predominant while on Ru or Pt, that of 1-cyclohexylethanol (CHE) prevails. By carefully designing the catalyst and selecting the reaction condition, one could obtain a very high yield of EB with only a small amount of side products. Based on the results, a bifunctional reaction mechanism was proposed.