Biomimetic composites were constructed using anorganic bone to initiate the polymerization of cyclic lactones. The resulting anorganic bone/polylactone composites preserve the inorganic structure and the mechanical properties of the original bone. Thermal conditions used to prepare the anorganic bone were shown to control the surface functionalities, surface area, and crystallinity, all of which influence the rates of subsequent polymerizations. Thermal pretreatment of anorganic bone was examined as a function of time and temperature, ranging from 400°C to 800°C. Polymerization rates of different monomers were also compared. Additionally, in vitro evaluations of anorganic bone/poly-l-lactide and anorganic bone/polyglycolide composites for osteoblast and osteoclast competence suggest that these composites are good candidates for potential in vivo use, since both composites promoted osteoblast differentiation. The anorganic bone/poly-l-lactide composite also promoted osteoclast differentiation. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 102A: 1755–1766, 2014.