We report herein the electrochemical dehalogenation of vicinal dibromides in microemulsions using cross-linked films of the redox protein myoglobin (Mb) and poly-L-lysine (PLL) covalently bonded to carbon electrodes. Catalytic reduction of the dibromides to olefins was more efficient in an SDS microemulsion than in a CTAB microemulsion. SDS shifts the Mb redox potential more negative, but a comparison to Mb-SDS films suggests that the activation free energy of the reduction is controlled by an inner-sphere mechanism. SDS also enters the positively charged Mb-PLL films and preconcentrates the dibromide reactants, enhancing catalytic efficiency in SDS microemulsions. Shifts in formal potential and Soret absorbance bands for Mb-PLL films suggested binding of trans-1,2-dibromocyclohexane in the iron heme distal pocket with little catalysis. Results are consistent with active catalytic reduction sites for reactant bound on the protein surface and less-reactive sites in the distal heme pocket. Preconcentration into catalytic PLL films using SDS incorporated from microemulsions may be a general way to improve catalytic efficiency for nonpolar reactants in microemulsions.