A simple suspension polymerization coupling with oxidative stabilization, carbonization, and H2O steam activation are applied to synthesize a series of hierarchical porous millimeter-sized pitch-based spherical activated carbons (PSAC). The as-obtained PSAC possess a tunable specific surface area from 975 m2 g− 1 to 1761 m2 g− 1, a pore volume of 0.44 ~ 0.82 cm3 g− 1, and spherical morphology via regulation of H2O activation time. The CO2 adsorption capacity is closely related to the ultramicroporous volumes below 0.2 bar. The introduction of rich micropores has a positively influence on CO2 adsorption capacity that can reach 2.59 mmol g− 1 at 1.0 bar. When the pressure increasing to 5.0 bar, the micro-mesoporous PSAC shows higher CO2 adsorption capacity of 7.23 mmol g− 1 at 5 bar than microporous PSAC, indicating that the introduction of moderate mesopores can accelerate CO2 diffusion rate and improve the utilization of micropores active adsorption sites. Based on the ideal adsorption solution theory (IAST), the CO2/N2 and CO2/H2O adsorption selection factors Sads of PSAC are as high as 49.9 and 8.29, respectively. Therefore, PSAC with high adsorption/desorption rate, good selectivity for CO2/N2 and CO2/H2O, excellent renewability, and easy mass production provide potential options for industrial application of CO2 capture.