Based on the basic theory of molecular recognition, we designed an organic molecules model that spontaneously form three-dimensional fibrillar scaffolds to induce the crystallization of hydroxyapatite to synthesized enamel-like calcium phosphate/hydroxyapatite under a controllable way in vitro. Cross-linking of collagen on the dentin surface and silk fibroin with N,N-(3-dimethylaminopropyl)-N'-ethyl-carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) was optimized by varying the NHS/EDC molar ratio at constant EDC concentration. CaCl2 and Na3PO4-12H2O solution was added with Ca: P odd as 1.67:1 after conjugated. The results showed that the dentinal tubule were blocked by neonatal hydroxyapatite layer which has a continuous structure of columns crystal with size of 10-40nm. Furthermore, there were column crystal with parallel direction inside, similar to the crystal array in the top of enamel rod. The results suggest that silk protein monolayer may be useful in the modulation of mineral behavior during in situ dental tissue engineering.