Photopolymerization reactions have been explored and utilized since the time of the ancient Egyptians; however, understanding of the basic formation-structure-property relationships have been severely lacking. Traditionally, photopolymerization of multifunctional monomers results in highly crosslinked materials suitable for applications as optical lenses, optical fiber coatings, and dental materials. These reactions are ubiquitous not only because of the nature of the final polymer product, but also for the characteristics of the reaction itself. Photopolymerizations are far more energy efficient than their thermal counterparts, are typically performed in a solventless manner that is more environmentally compatible, the reactions occur rapidly at ambient conditions, and the polymerization can be controlled in both time and space. Further, the advent of novel photopolymerization mechanisms and materials has complicated these systems while also enabling unparalleled potential in the range of processing conditions that can be used, the polymer material properties that can be attained, and the unique applications to which photopolymerization can now be applied. Here, we will survey work over the last 15 years that builds from the fundamental kinetic and structural evolution theories through the advent and development of two new polymerization strategies to the ultimate application of these materials in tissue engineering matrices, liquid crystal devices, and dental materials. Here, we will focus on three distinct vignettes related to our photopolymerizations work including the basic theoretical framework used for modeling the photopolymerization reaction and the evolving polymer structure, the development of novel thiol-ene photopolymerization reactions and materials, and the application of photopolymerization technology to novel applications including biological agent detection, development of novel photoplasticizable materials and the development of low stress, highly crosslinked polymers.