Injectable hydrogels are quite promising materials due to their potential to minimize invasive implantation and this provides versatile fitness irrespective of the damaged regions and facilitates the incorporation of bioactive agents or cells. In situ gel formation through stereocomplex formation is a promising candidate for injectable hydrogels. In this paper, a new series of enantiomeric, four-arm, PEG-PLA block copolymers and their stereocomplexed hydrogels were prepared by bulk ring-opening polymerization of D-lactide and L-lactide, respectively, with stannous octoate as a catalyst. The prepared polymers were characterized by 1H nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared (FT IR) spectroscopy, gel permeation chromatography (GPC) and thermal gravitational analysis (TGA), confirming the tailored structure and chain lengths. The swelling and degradation behavior of the hydrogels formed from a selected copolymer series were observed in different concentrations. The degradation rate decreased with increasing polymer content in the solution. The rheological behavior indicated that the prepared hydrogel underwent in situ gelation and had favorable mechanical strength. In addition, its feasibility as an injectable scaffold was evaluated using a media dependence test for cell culture. A Tris solution was more favorable for in situ gel formation than PBS and DMEM solutions were. These results demonstrated the in situ formation of hydrogel through the construction of a stereocomplex with enantiomeric, 4-arm, PEG-PLA copolymers. Overall, enantiomeric, 4-arm, PEG-PLA copolymers are a new species of stereocomplexed hydrogels that are suitable for further research into injectable hydrogels.