Vaterite-containing β-dicalcium silicate powder (A-V-CS) was successfully grafting modified by 3-aminopropyltriethoxysilane (APTES) through reflux agitation. The purpose of this work is to fix the amino groups on the vaterite-containing β-dicalcium silicate (V-CS) powder's surface, which makes the powder's surface with positive charge, and further enhanced the combination with those negatively charged bioactive molecules or drugs to improve the performance of biomaterials. XRD and FT-IR analysis indicated that N-H groups were successfully grafted onto the surface of the V-CS sample on the basis of vaterite existence through the process of first grafting then carbonation. Moreover, the best grafting modification that refluxing at 70 °C for 12 h was determined through the quantitative analysis of N-H groups on V-CS powder's surface. The A-V-CS sample showed a better apatite formation ability after it was soaked in stimulated body fluid (SBF), indicating that good apatite mineralization. Moreover, the A-V-CS sample with weak alkali in implanting position could stimulate the attachment, proliferation and improve the activity of MC3T3-E1 cells. Experimental results demonstrated that, A-V-CS was expected to be a new biomaterial as bone repairing substitute.