The crosslinking behaviors and gelation features of poly(ethylene glycol) (PEG) hydrogels were scrutinized during the UV and thermal polymerizations of mixtures of poly(ethylene glycol) methacrylate (PEGMA, monomer) and poly(ethylene glycol) dimethacrylates (PEGDMAs, crosslinkers). The real-time crosslinking behavior of the PEG hydrogels was quantified as a function of the UV irradiation time and reaction temperature during the UV and thermal polymerization, respectively, using real-time FT-IR spectrometry and rotational rheometry. The gelation characteristics of UV- and thermally crosslinked hydrogels were compared through the analysis of the gel fraction, swelling ratio, surface hardness, and the loading and release of rhodamine-B. The gelation properties of the cured hydrogel films were suitably correlated with the real-time rheological properties and crosslinked network state of the PEG mixtures. The crosslinking and gelation properties of the cured hydrogels could be optimally tuned by not only the molecular weight of the crosslinker but also the UV or thermal polymerization conditions.