In the present study, the effects of pH and initial Ca2+-H2PO4- (Ca-P) concentration on fibroin mineralization were studied. The crystal growth of calcium phosphates was regulated by regenerated silk fibroin for 8 h (at pH 4.0, 7.0 and 10.0, respectively). Meanwhile, different concentrations of Ca2+ were employed at a certain pH value, keeping the initial Ca-P molar ratio constant at 1.67, i.e., the stoichiometry of hydroxyapatite [Ca10(PO4)6(OH)2, HAP]. The products were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The results demonstrated that, compared to pH 4.0 and 10.0, pH 7.0 promoted the transformation of brushite (CaHPO4°2H2O, DCPD) to HAP. In the composites of mineralized fibroin, DCPD is the main inorganic phase at both relatively low and high pH, while HAP is the main inorganic phase at pH 7.0. Additionally, the initial Ca-P concentration does not affect the kind of inorganic phase in the synthesized mineralized fibroin, but induce to different contents of inorganic mineral and different morphology of DCPD at pH 4.0 and pH 10.0.