The combination of multiple physical properties is of great importance for widening the application scenarios of biomaterials. It remains a great challenge to fabricate biomolecules‐based fibers gaining both mechanical strength and toughness which are comparable to natural spider dragline silks. Here, by mimicking the structure of dragline silks, a high‐performance fluorescent fiber Alg‐TPEA‐PEG is designed by non‐covalently cross‐linking the polysaccharide chains of alginate with AIEgen‐based surfactant molecules as the flexible contact points. The non‐covalent cross‐linking network provides sufficient energy‐dissipating slippage between polysaccharide chains, leading to Alg‐TPEA‐PEG with highly improved mechanical performances from the plastic strain stage. By successfully transferring the extraordinary mechanical performances of polysaccharide chains to macroscopic fibers, Alg‐TPEA‐PEG exhibits an outstanding breaking strength of 1.27 GPa, Young's modulus of 34.13 GPa, and toughness of 150.48 MJ m−3, which are comparable to those of dragline silk and outperforming other artificial materials. More importantly, both fluorescent and mechanical properties of Alg‐TPEA‐PEG can be well preserved under various harsh conditions, and the fluorescence and biocompatibility facilitate its biological and biomedical applications. This study affords a new biomimetic designing strategy for gaining super‐strong, super‐stiff, and super‐tough fluorescent biomaterials.