Near-infrared (NIR) laser has deeper penetration and lower thermal effect compared with ultraviolet-visible (UV/vis) laser. NIR laser can stimulate upconversion nanoparticles (UCNPs) to emit UV/vis light efficiently. Therefore, the UCNPs become an important kind of materials to produce upconversion luminescence through NIR laser. Compared with photopolymerization induced with UV/vis laser, the UV/vis light from UCNP-assisted photopolymerization presents some unique characters. This review focuses on the research progress of UCNP-assisted photopolymerization and its potential applications. We will discuss the influencing factors of UCNP-assisted polymerization, illustrate the relation between the gel size and monomer concentration and propose the development prospects of UCNP-assisted polymerization in the biological field.