Bone defects and injuries are challenging issues in regenerative medicine. Guided bone regeneration (GBR) techniques use biomaterials as scaffolds to support the healing of damaged bone tissue. In this context, there is growing interest in developing new biomaterials with bioabsorbable and bioactive properties to increase GBR effectiveness. In this study, composite corn starch/hydroxyapatite nanoparticle (HAp) biomembranes were synthesized to achieve bioresorbable and bioactive properties compatible with applications in GBR. Starch is a renewable source and presents suitable rheological properties for membrane preparation; in turn, HAp is well known for its osteogenic properties. The biomembranes were prepared by solvent casting (5 wt% aqueous corn starch suspension containing different amounts of HAp (i.e., 0, 2, 5, and 10% of the corn starch weight), to give the membranes HAp_0%, HAp_2%, HAp_5%, and HAp_10%, respectively). The physicochemical and biological properties of the biomembranes were assessed. The concentrations of up to 10% of HAp were homogeneously dispersed in the composite biomembranes. HAp addition increased the biodegradability and the ability of the biomembranes to release Ca2+. The biomembranes containing HAp were more mechanically resistant and less flexible and were not toxic to osteoblasts. Moreover, compared to pure corn starch biomembranes, osteoblasts adhered better to the composite biomembranes. The higher the HAp content, the greater the mineralization promoted by osteoblasts on the composite biomembranes. HAp addition also resulted in composite biomembranes with better fracture healing efficiency in vitro. Therefore, composite corn starch/HAp biomembranes have excellent characteristics, including biodegradability, bioactivity, mechanical strength, and biocompatibility, for the development of new materials aimed at GBR.