Abstract 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.