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[Display omitted] • Two new PIMs were synthesized and applied for CO 2 capture. • High CO 2 working capacity was obtained. • Good dynamic CO 2 /N 2 mixture separation performance was obtained. • A dissolution-separation-precipitation (DSP) approach was proposed and proved. • Distinguished renewability after fouling. Anthropogenic carbon dioxide emission has been an urgent environmental and climate issue, yet remains a challenge to address. Solid adsorbents are potential candidates for CO 2 capture while their insolubility nature makes the regeneration problematic when fouled. Here we report the synthesis of a thioamide incorporated polymer of intrinsic microporosity, TPIM, which features high intrinsic microporosity with specific surface areas of 531 m2/g, and good solubility in selected organic solvents such as THF, DMSO and DMAc. Static physisorption and kinetic breakthrough experiments revealed several promising features of TPIM: high CO 2 capacity of 2.45 mmol/g at 1 bar and 298 K, good CO 2 /N 2 mixture dynamic separation performance, and facile regeneration ability. Most interestingly, its porosity and CO 2 capacity could be easily restored through a simple dissolution-separation-precipitation (DSP) approach, making it regenerative when fouled, providing a new insight for the future design of regenerable adsorbents. [ABSTRACT FROM AUTHOR]