We report an operationally simple protocol for the catalytic alpha-deuteration of styrenes. This process proceeds via the base-catalyzed reversible addition of methanol to styrenes in DMSO-d(6) solvent. The concentration of methanol is shown to be critical for high yields and selectivities over multiple competing side reactions. The synthetic utility of a-deuterated styrenes for accessing deuterium-labeled chiral benzylic stereo-centers is demonstrated.