Smart delivery systems have received increasing attentions, due to the controllable capturing-releasing of the guests in many applications. Here, we propose a pH-responsive Au cluster capturing-releasing system using the mesoporous silica nanoparticles (MSNs) modified by organic molecular tweezers. The pi-pi-pi stacking have been used to capture and stabilize the Au clusters in the pores of MSNs on the neutral or alkaline conditions, and responsively release and manipulate the Au clusters by adjustment of the pH value. The released Au clusters show high catalytic activity.