Segmental mandibular defects are a common problem in head and neck surgery. Osseous free flap transfer has revolutionized mandibular reconstruction; however, donor site morbidity remains a significant problem. Bone tissue engineering (BTE) employs strategies for reconstructing critical-sized bone defects, improving the patients’ quality of life. Scaffolds employed for BTE must be mechanically stable, osseointegrate with neighboring bone, and promote osteogenesis. The need for modified, hybrid constructs with a diversity of favorable characteristics is essential. This review focuses on the recent progresses in modulating the physiochemical properties and applications of biomaterials in BTE in the context of mandibular segmental defect repair.