We report a facile but general method to prepare highly water-soluble and biocompatible photoinitiators for digital light processing (DLP)-based 3D printing of high-resolution hydrogel structures. Through a simple and straightforward onepot procedure, we can synthesize a metal-phenyl(2,4,6trimethylbenzoyl)phosphinates (M-TMPP)-based photoinitiator with excellent water solubility (up to ∼50 g/L), which is much higher than that of previously reported water-soluble photoinitiators. The M-TMPP aqueous solutions show excellent biocompatibility, which meets the prerequisite for biomedical applications. Moreover, we used M-TMPP to prepare visible light (405 nm)-curable hydrogel precursor solutions for 3D printing hydrogel structures with a high water content (80 wt %), high resolution (∼7 μm), high deformability (more than 80% compression), and complex geometry. The printed hydrogel structures demonstrate great potential in flexible electronic sensors due to the fast mechanical response and high stability under cyclic loadings.