Intrinsic self-healing soft materials such as hydrogels are especially promising for a variety of medical applications. Multistep preparation of starting functional polymer precursors and the expensive stock materials such as tetra-polyethylene glycol are one of the factors that limit the wider use of self-healing hydrogels. Herein, we reported a facile one-pot approach to prepare PEG based self-healing hydrogels from inexpensive commercially available components: polyethylene glycol diacrylate and dithiothreitol. For the first time, borax was used as the catalyst for a thiol-ene Michael-type polyaddition of PEG gels. Borax as the catalyst is quite efficient, allowing rapid gelation (from 40 s to 2 min) under ambient conditions and at room temperature. Essentially, as one catalyst, borax induces the formation of two classes of bonds, covalent thioether and transient boronate ester bonds, were formed at the same time. The storage modulus of the afforded PEG gel (87.5% water) reached up to 104 Pa, making the mechanical performance comparable with permanently cross-linked PEG gels. Additionally, the dynamic nature of the boronate ester linkages imparts the gel with self-healing properties, and the obtained gels can be healed within 30 min without external stimulus. Further, the transparent hydrogel is pH and thermal responsive. We believe that the manifold impacts of borax can open a new route to prepare hydrogels with intriguing properties, which find potential application as gel sealant, biosensors, or regenerative medicines.