The skull provides protection and mechanical support, and acts as a container for the brain and its accessory organs. Some defects in the skull can fatally threaten human life. Many efforts have been taken to repair defects in the skull, among which cranioplasty is the most prominent technique. To repair the injury, numerous natural and artificial materials have been adopted by neurosurgeons. Many cranioprostheses have been tried in the past decades, from autoplast to bioceramics. Neurosurgeons have been evaluating their advantages and shortages through clinical practice. Among those prostheses, surgeons gradually prefer bionic ones due to their marvelous osteoconductivity, osteoinductivity, biocompatibility, and biodegradability. Autogeneic bone has been widely recognized as the "gold standard" for renovating large-sized bone defects. However, the access to this technique is restricted by limited availability and complications associated with its use. Many metal and polymeric materials with mechanical characteristics analogous to natural bones were consequently applied to cranioplasty. But most of them were unsatisfactory concerning osteoconductiion and biodegradability owe to their intrinsic properties. With the microstructures almost identical to natural bones, mineralized collagen has biological performance nearly identical to autogeneic bone, such as osteoconduction. Implants made of mineralized collagen can integrate themselves into the newly formed bones through a process called "creeping substitution". In this review, the authors retrospect the evolution of skull repair material applied in cranioplasty. The ultimate skull repair material should have microstructure and bioactive qualities that enable osteogenesis induction and intramembranous ossification.