Acrylate chemistry has found widespread use in dual-curing systems over the years. Acrylates are cheap, easily handled and versatile monomers that can undergo facile chain-wise or step-wise polymerization reactions that are mostly of the “click” nature. Their dual-curing processes yield two distinct and temporally stable sets of material properties at each curing stage, thereby allowing process flexibility. The review begins with an introduction to acrylate-based click chemistries behind dual-curing systems and relevant reaction mechanisms. It then provides an overview of reaction combinations that can be encountered in these systems. It finishes with a survey of recent and breakthrough research in acrylate dual-curing materials for shape memory polymers, optical materials, photolithography, protective coatings, structured surface topologies, and holographic materials