Herein, we prepared a series of hollow hyper-cross-linked polymer (HCP) microspheres with a hollow core shell structure via the hard-template method, and the as-prepared HCPs were employed for rhodamine B (RB) adsorption and CO2 capture. The results indicate that the porosity of the HCPs can be easily tuned and the hollow microspheres are favorable for the fast mass transfer of RB in the pore channels; accordingly, the adsorption equilibrium can be attained quickly. In addition, the hollow microspheres are helpful for increasing the equilibrium capacity. The RB adsorption shows that HCPs-5% holds the best capacity (1400 mg/g) and acceptable equilibrium time (60 min). On the other hand, the CO2 adsorption exhibits that HCPs-5% holds the highest CO2 uptake (99.0 mg/g) and the ultramicropores play important roles in the adsorption. The HCPs hold moderate isosteric heat of CO2 adsorption (24.4-35.0 kJ/mol) and exhibit excellent recycling performance.