Silk fibroin (SF) has the characteristics of non-toxicity, good biocompatibility and low immunogenicity, and exhibits many potential applications in biomaterial fields. In the present work, chemical phosphorylation of SF was carried out via the Maillard reaction using D-glucose-6-phosphate (GP), aiming at increasing the number of binding-sites for calcium ion and promoting the biomimetic mineralization of SF films. Changes in the molecular weight of SF before and after GP grafting were analyzed by SDS-PAGE and SEC chromatogram. Structures, morphologies, and elemental compositions for the fibroin-based films before and after mineralization were evaluated by the means of EDS, SEM, FTIR, and XRD. The results indicated that GP was successfully grafted onto SF surfaces, companying with a slight decrease in the molecular weight. Biomimetic mineralization led to a noticeable deposition of hydroxyapatite (HAp) on the film of SF-g-GP, and higher contents of calcium and phosphorous were detected on the mineralized material, revealing that phosphorylation promoted the mineralization processing. Meanwhile, biocompatibility of the obtained SF-g-GP/HAp was above the acceptable level according to ISO 10993-5-2009. The present work provides an alternative to prepare the fibroin-based bone repair materials.