Abstract Biocompatible, tough, and photoluminescent hydrogels are highly desirable for biomedical applications in vivo. Herein, hybrid hydrogels prepared from silk fibroin (SF) and polyacrylic acid (PAA) and complexed with europium, named as SF‐PAA‐Eu 3+ hydrogels, exhibit good comprehensive properties. Owing to the intensive molecular interactions among SF, PAA, and Eu 3+ , SF‐PAA‐Eu 3+ hydrogels show a greatest tensile strength of 0.58 MPa, elongation of 443%, and work of fracture of 1.65 MJ/m. In vivo imaging experiment in a mouse subcutaneous implantation model revealed excellent and sustained photoluminescence of the SF‐PAA‐Eu 3+ hydrogels for 24 h. The work provides a strategy for designing functional SF‐based hydrogels for imaging applications in vivo.