Light-responsive metal-organic frameworks (LMOFs) are intriguing materials for CO2 capture owing to their tunable structures and performances. However, conventional LMOFs are reported to regulate CO2 adsorption capacity by steric hindrance or structural variation because of the weak affinity between the adsorbate and adsorbent. Developing efficient LMOF-based adsorbents with strong but tunable active sites for controllable CO2 capture is an extremely desirable yet challenging task. In this work, we constructed an LMOF-based adsorbent with targeted adsorption sites by incorporating polyethyleneimine into an azobenzene-decorated LMOF for controllable CO2 capture. The targeted active sites of amines endow the adsorbent with enhanced selectivity in the capture of CO2. Additionally, the surface electrostatic potential around amines can be regulated by the isomerization of azobenzene moieties upon light irradiation. Moreover, the reversible light irradiation generates the adsorbents with exposed/sheltered adsorption sites for the controllable capture of CO2 on amines. The present work encourages us to develop novel LMOF-based adsorbents for controllable adsorption separation, which is hard to realize by conventional LMOFs.