Among the different types of specialty polymers, polysiloxane finds its position in the pyramid's apex in terms of its performance attributes. Its unique structural features result in it having superior performance benefits over wide operational conditions. Hence, polysiloxanes are used in various industries. Like other polymers, to effectively use polysiloxanes, curing is a non-negotiable fact. Therefore, polysiloxanes are cured using different chemistries such as addition, condensation, and peroxy-mediated methods, etc. However, recently, it has been noted that there is a strong impetus towards developing radiation-curable polysiloxanes. A faster turnover time, higher yield, and marginal involvement in the release of any toxic by-products has resulted in the widespread acceptance of radiation curing techniques. This review article provides insight into the various facets of polysiloxane chemistry, the synthesis of radiation curable polysiloxane, and the curing methodology of polysiloxane using radiation sources such as ultraviolet, electron beam, and gamma radiation. We further provide an account of the various applications of such radiation-curable polysiloxanes.