This study presents and evaluates an approach for fabricating poly(lactic acid) (PLA)/chitosan (CS)/tricalcium phosphate (TCP) electrospun scaffolds for guided bone regeneration, a dental procedure that uses membranes to direct and delineate regions of osteogenesis. Biomaterials were pre‐processed using cryomilling, a solid‐state grinding technique that facilitates the generation of powdered biocomposites conducive to electrospinning. X‐ray diffraction (XRD) confirmed the generation of cryomilled blends consisting of PLA, CS, and TCP. Results from the differential scanning calorimetry showed an upward shift in glass transition temperature and an increase in crystallinity with the inclusion of TCP reinforcing the observations from XRD. Murine macrophages were used to confirm the biocompatibility of the cryomilled powders and was evaluated using CellTiter‐Blue (CTB) cell viability assay and brightfield microscopy. Scanning electron microscopy was used to examine the morphology of the fibers produced via electrospinning, while Raman spectroscopy confirmed material homogeneity. In vitro studies with MG‐63 cells validated the capacity of composite scaffolds to encourage proliferation, while Coherent anti‐Stokes Raman scattering and fluorescence microscopies provided visual evidence of cell proliferation. CTB assay revealed that cells maintain viability and metabolic activity at 3 and 7 days after seeding, demonstrating the potential of the biocomposite membranes.