A controlled release system with pH-responsive ability has been presented. Mesoporous bioglass (MBG) was used as the drug carrier and a spontaneous mineralization method was adopted to cap the pores of the carrier with hydroxyapatite (HAp) and to restrict the drug release. It is a simple and green method to realize the ingenious pH-sensitive controlled release. The model drug, metformin hydrochloride (MH), was loaded simultaneously with the mineralization process. Due to the degradation of HAp at acid environments, the system shows well pH-sensitive drug release ability. The release kinetics can be easily adjusted by the mineralization time and the ion concentration of media. The system is recommended as a promising candidate as a pH-sensitive vehicle for drug controlled release to low pH tissues, such as inflammatory sites and tumors.