Although efficient light delivery is required for various biomedical applications, the high stiffness of traditional silica‐based optical fibers limits their in vivo usage. In this study, highly deformable and stretchable soft optical fibers are prepared based on the mechanically tough hydrogels of a double network (DN) structure comprising covalently crosslinked acrylamide and ionically crosslinked alginate using a microfluidic device. Owing to the optimized chemical composition, the core/cladding structure, and the mechanical robustness of the prepared hydrogel optical fibers, highly efficient optical delivery is achieved even at highly deformed and elongated states. Furthermore, the microfluidic device further allowed the formation of dual‐core, novel architectures for hydrogel optical fibers. With the aid of the dopamine moiety included in the cladding, the hydrogel optical fibers attached strongly to all surfaces tested. Light delivery is further confirmed by implantation in the biological tissues. The high light‐guiding performance of the developed hydrogel optical fibers enables them to replace the conventional silica optical fibers used in UV/Vis, fluorescence, and photoacoustic spectroscopies. To demonstrate their in vivo fiber‐optic application potential, they are placed inside mice, and the excitation and emission of the generated fluorescence signals are detected.