This review aimed to examine the evolution of the composite resins`s photoinitiator system, with emphasis on those developed in recent years. This review covered literature from 1990 to 2013 and only papers with the key words of interest were included: "coinitiators", "amines", "composite resins", "photopolymerization". The search used full-text papers from PubMed and Science Direct databasis. It was included only English papers, and meeting abstracts and short communications were excluded. Hand search of the references completed the review. A total of 29 articles were studied. Many coinitiators are being researched as an alternative to traditional tertiary amines, particularly in order to improve the physical and mechanical properties of the final polymer and its biocompatibility with oral tissues. Polymerizable amines, natural compounds, and coinitiators with low toxicity and antiseptic properties were studied, and the results found they would be promising substitutes. These materials must present appropriate concentration and reactivity to obtain adequate physical and mechanical properties and high biocompatibility. However, further in vivo studies are required to verify the performance of these alternative coinitiators in the composite materials, mainly when in contact with oral tissues and the stomatognathic system.