A series of triphenylamine-functionalized phthalazinone-based covalent triazine framework materials (PHCTF-8) with high specific surface areas were successfully designed and constructed from a novel, centrosymmetric, and pinwheel-like tricyano precursor (TPAHPZ-TN) by ionothermal polymerization. The tricyano building blocks can be easily prepared by a simple and low-cost aromatic nucleophilic substitution reaction, and the rigid and twisted phthalazinone moiety offers the support to the porous structure. Additionally, three functional groups increased the crosslinking density, providing effective division of the space and enhancing the thermal stability of these polymer networks. Furthermore, the high specific surface area, superior porosity with dominated microporous distributions and electron-rich N-heterocycle skeleton feature lead to a high CO2 storage capacity of the PHCTF-8 of up to 17.8 wt% at 273 K and 1 bar, a very competitive capacity of 11.2 wt% (2.55 mmol/g) at 298 K and 1 bar, and a high capacity at low pressures (4.3-5.7 wt%, 0.15 bar at 273 K). Therefore, the excellent gas storage capacity, accompanied by CO2/N-2 selectivity calculated by the ideal solution theory (IAST) up to 142 (273 K) for the high V-micro and electron-rich character, together with the easily scaled-up preparation method of the building blocks and polymer networks, impart porous materials with high specific surface area having promising application potential for CO2 separation technology. (C) 2018 Elsevier Ltd. All rights reserved.