Theories on the origin of life suggest that homochiral biopolymers were already being generated in prebiotic times from racemic mixtures of activated monomeric precursors; [1][2][3] various scenarios for their formation have been proposed. [4][5][6][7] In our current program we promote a conceivable scheme for the formation of primitive homochiral polymers from mixtures of racemates or nonracemic mixtures of low enantiomeric imbalance, by their self-assembly within twodimensional (2D) or 3D crystalline architectures of distinct packing motifs, followed by lattice-controlled polymerization reactions.[8-10] The overall process entails two different aspects: a) Generation of racemic mixtures of homochiral polymers from racemates, and b) only one of the two enantiomeric polymers are formed by spontaneous symmetry breaking or by asymmetric induction.Polymerization reactions within rigid 3D crystals, initiated either thermally or by irradiation, are controlled by the crystal lattice, to the greatest extent, at the onset of the reaction, since the polymeric phase produced is generally much denser than the crystalline monomer reactant. Changes in density and heat release that occur at sites of chain propagation induce local disorder, which brings about the formation of nonstereospecific polymers. Consequently, after years of research, only a limited number of systems including dieth-