Exploring　photoluminescent　silk　fibers,　possessing　biocompatibility　as　well　as　stable　and　durable　fluorescent　properties,　is　a　requirement　for　the　development　of　novel　photoluminescent　biomaterials.　Herein,　we　fabricate　photoluminescent　silk　fibers,　TPCA@SF,　via　modifying　an　organic　fluorescent　molecule　(5-oxo-3,5-dihydro-2H-thiazolo　[3,2-a]　pyridine-7-carboxylic　acid,　TPCA)　onto　silk　fibers,　along　with　using　quaternary　ammonium　salt　didodecyldimethylammonium　bromide　(DDAB)　as　a　color-fixing　agent.　The　hydrogen　bonds　and　electrostatic　association　among　silk　fibers,　TPCA　and　DDAB,　ensure　the　stable　modification.　The　facile　and　green　fabrication　process　is　achieved　in　water　under　mild　conditions　without　using　any　toxic　substances.　The　TPCA@SF　manifests　the　combining　features　of　high　quantum　yield,　fluorescence　water-fastness,　antiphotobleaching,　good　mechanical　property,　and　biocompatibility.　The　strategy　holds　great　potential　for　exploring　various　biocompatible　photoluminescent　substances　with　stability　and　durability.