Photopolymerization is used in a wide range of clinical applications in dentistry and the demand for dental materials that can restore form, function and esthetics is increasing rapidly. Simultaneous with this demand is the growing need for photoinitiators that provide effective and efficient in situ polymerization of dental materials using visible light irradiation. This chapter reviews the fundamentals of Type I and II photoinitiators. The advantages and disadvantages of these photoinitiators will be considered with a particular focus on parameters that affect the polymerization process in the oral cavity. The chapter examines recent developments in photoinitiators and opportunities for future research in the design and development of photoinitiators for dental applications. Future research directions that employ computational models in conjunction with iterative synthesis and experimental methods will also be explored in this chapter.