Nanogel is an important kind of biomaterials applied for wound dressings, drug delivery, medical diagnostics and biosensors. The properties of nanogels closely depend on the density of the crosslinking network. In this study, the role of triethanolamine (TEOA) in the effect on the crosslinking degree of nanogels based on poly(ethylene glycol) diacrylate (PEGDA) was investigated and illustrated. The effect of TEOA on the process of photopolymerization at 532 nm and properties of the nanogels was systematically investigated by using UV‐vis spectroscopy, FT‐IR spectroscopy, 1H NMR, DLS, SEM, AFM and DSC. In brief, the double‐bond conversion of photopolymerization and the crosslinking degree of nanogels can be effectively regulated by TEOA.