A method for the organocatalytic, highly enantioselective, and moderately diastereoselective dimerization (redox isomerization/acetal formation) of γ‐hydroxyenones is disclosed. The stereogenic acetal products were obtained via hemiacetal intermediates followed by a cyclization reaction. With bifunctional thiourea catalysts, high yields and excellent enantioselectivities were achieved for a variety of acetal products under mild reaction conditions. In addition, detailed DFT calculations were performed to investigate the mechanism of this reaction, and these calculations suggested that the diastereoselectivity was due to a kinetically controlled process.