With the advantages offered by cationic photopolymerization (CP) such as broad wavelength activation, tolerance to oxygen, low shrinkage and the possibility of “dark cure”, it has attracted extensive attention in photoresist, deep curing and other fields in recent years. The applied photoinitiating systems (PIS) play a crucial role as they can affect the speed and type of the polymerization and properties of the materials formed. In the past few decades, much effort has been invested into developing cationic photoinitiating systems (CPISs) that can be activated at long wavelengths and overcome technical problems and challenges faced. In this article, the latest developments in the long wavelength sensitive CPIS under ultraviolet (UV)/visible light-emitting diodes (LED) lights are reviewed. The objective is, furthermore, to show differences as well as parallels between different PIS and future perspectives.