Postoperative adhesions occur in over 90% of all surgeries resulting in life-altering medical complications that impact millions of people every year. Surgical intervention to prevent them often result in their reoccurrence, creating a clinical need for preventative methods immediately post-operation. Their formation is thought to be governed by a complex biological interplay that renders purely therapeutic preventatives impractical. The several United States Food and Drug Administration approved products often fail to demonstrate safety and efficacy across the diverse tissue complexes that exhibit postoperative adhesions. The usage of therapeutics and physical barriers for their prevention, including biomaterials, has recently expanded to incorporate numerous new small molecule components and chemistries. Here, we summarize the adhesions problem from a clinical and biological standpoint before reviewing the currently ongoing research and development of potential new prevention methodologies. The efficacies of several of these multi-functional materials highlight the need for a synergistic approach in design of prevention strategies, which can be enhanced by further understanding of the formation causes and mechanisms.