Abstract5‐Methacryloyl‐ and 5‐isobutyrylaminosalicylaldehydes (5aand5b, respectively) and diastereomeric complexes of their Schiff bases with amino acids and Co(III): potassium Λ‐ and Δ‐bis‐[N‐5‐methacryloylaminosalicylidene‐(S)‐valinato]cobaltate(III) (6a,b), potassium Λ‐ and Δ‐bis[N‐5‐isobutyrylaminosalicylidene‐(S)‐norvalinato]cobaltate(III) (7a, b), potassium Λ‐ and Δ‐bis[N‐5‐methacryloylaminosalicylidene‐(S)‐norvalinato]cobaltate(III) (8a, b), have been synthesized. Copolymerization of6–7a, bwith acrylamide andN,N′‐methylenebis(acrylamide) leads to the formation of transparent hydrophilic gels in which the amino acid fragments preserve their ability of exchanging α‐hydrogen for deuterium in an alkaline medium. Comparison of the behaviour of polymer complexes ℗‐7aand ℗‐7bin the process of base‐catalyzed epimerization with their monomer analogues8aand8bshows that their stereoselectivity substantially changes when one goes from8ato ℗‐7a. Such an effect may be explained by stabilization of the initial conformation of the complex molec