The removal of an eye is one of the most difficult and dramatic decisions that a surgeon must consider in case of severe trauma or life-threatening diseases to the patient. The philosophy behind the design of orbital implants has evolved significantly over the last 60 years, and the use of ever more appropriate biomaterials has successfully reduced the complication rate and improved the patient's clinical outcomes and satisfaction. This review provides a comprehensive picture of the main advances that have been made in the development of innovative biomaterials for orbital implants and ocular prostheses. Specifically, the advantages, limitations and performance of the existing devices are examined and critically compared, and the potential of new, smart and suitable biomaterials are described and discussed in detail to outline a forecast for future research directions.