Biocatalysis in bicontinuous microemulsions is a promising approach for synthetic routes to regio- and stereoselective and efficient synthetic processes. Redox enzymes such as peroxidases and monooxygenases can be attached to surfaces for biocatalysis and operated in low toxicity microemulsions to enhance the dissolution of non-polar reactants, but still provide a water rich environment for the enzyme catalysis resulting in high product yield and chiral products. Here we report a new hybrid electrocatalyst system for biocatalysis using a synthetic Cu-polymer catalyst deposited on an electrode and cross-linked films of poly(L-lysine) (PLL) and redox enzymes horseradish peroxidase (HRP) and cytochrome P450 (Cyt P450) in films on oxidized pyrolytic graphite (PG) electrodes or carboxylate functionalized magnetic particles. Enzymes in these catalytic films are activated by O2 conversion to H2O2 by the Cu polymer. In microemulsions, enzyme reactions occur in a water-rich film environment with delivery of non-polar reactants from the oil-rich regions of the microemulsion. Reactions can be achieved that cannot be run in water due to lack of reactants solubility. Rotating-disk voltammetry (RDV) was used to assess catalytic activity of cross-linked enzyme/PLL films in the presence of H2O2. Activity of cross-linked HRP on magnetic particles was similar to that of 3 mg/mL of free HRP, and these HRP-beads can be used for synthesis up to 95 °C. Oxidation of 2-naphthol by HRP/PLL coated magnetic particles in microemulsions resulted in (R)- and (S)-1,1’-Bi-2-naphthol with chiral ratio determined by chiral HPLC. High product yields of oxidation products were achieved at 80 °C than 20 °C, with product analysis suggesting increasing catalytic efficiency and selectivity at higher temperatures. Additional chiral HRP reactions will be described, and cross-linked Cytochrome P450s are also being explored for stereoselective oxidation and hydroxylation of substrates including styrene, ethyl benzene and 1-tetralone.