There is a great challenge in constructing pH-responsive drug delivery systems in biomedical application research. Many nanocomposites are intended to be pH-responsive as drug carriers because of a tumorous or intracellular mildly acidic environment. However, it is always difficult to find an appropriate system for quick response and release before the carrier is excreted from the living system. In this work, hyperbranched polymer, hyperbranched polyglycerol (hPG), and conjugated mesoporous silica nanoparticles (MSNs) were assembled as complexes to serve as drug carriers. Herein, the conjugated polymer-MSNs interacted through the Schiff base bond, which possessed a mildly acidic responsive property. Interestingly, the assembled system could rapidly respond and release guest molecules inside cancer cells. This would make the entrapped drug released before the carriers escape from the endosome counterpart. The results show that the assembled composite complexes can be considered to be a drug delivery system for cancer therapy.