In tissue engineering applications the physical properties and degradation behavior of the designed synthetic scaffold are crucial for successful growth and function of desired tissue. Combining two or more biodegradable polymers into a single biomaterial composite may provide a pathway toward achieving new and highly tailorable biomaterial properties by taking advantage of the distinct properties from each blend component. In this work, a nanostructured lyotropic liquid crystal (LLC) was used to induce miscibility between blends of two immiscible biodegradable polymer systems, leading to the formation of a compatible composite with advanced properties. The physical properties and degradative behavior of biomaterials made from formulations of PLA-b-PEG-b-PLA dimethacrylate, caprolactone dimethacrylate, and ethyloxy succinate dimethacrylate were directly controlled using the composition of each material, demonstrating that a high degree of compatibility can be attained from immiscible biopolymer systems using the LLC polymerization template. Specifically, by initially confining the immiscible monomers into the nanometer scale domains of the liquid crystal, composite materials were formed upon cross-linking that demonstrated IPN-type behavior with linear or additive contributions from each biopolymer constituent. The use of a nanostructured LLC to compatibilize, immiscible biodegradable monomers represents a significant advancement in the formation of cross-linked biocomposites with highly tailorable properties for tissue engineering applications.