This paper reviews the field of cationic UV‐curing and reports recent progress made in understanding the fundamental chemistry and in technology applications. Radiation curing technologies are expanding rapidly on an industrial scale and interest in cationic photopolymerizations has advanced rapidly. In particular, the cationic UV‐curing process presents additional benefits, including: the absence of air inhibition, a “dark‐curing” reaction, low levels of toxicity and irritation, and a lower volume shrinkage during photopolymerization. In this review, a large number of papers and patents are reviewed and critically discussed specifically with respect to the application of cationic UV‐curing technology in the field of coatings, composites, adhesives, and inks.