A series of multifunctional nanoporous organic polymers with high microporosity have been successfully synthesized via Friedel-Crafts alkylation and Scholl coupling reactions. Porous properties are well-controllable by simply regulating the lengths and rigidities of linkers, where the rigid tetrahedral building block, i.e. 1,3,5,7-tetraphenyladamantane, knitted with flexible alkyl chains leads to a hierarchically porous structure of NOP-53. Such amorphous materials derived from the high rigid building block achieve high surface areas (1178 m(2) g(-1) for NOP-54) and substantially improved micro-pore volumes (0.86 cm(3) g(-1), V-micro/V-total = 65%). The as-made porous network NOP-54 featuring highest microporosity can uptake 14.2 wt% CO2 at 273 K and 1 bar, and good selectivity ratios for CO2 adsorption over N-2 (56.1) and CH4 (13.9) at 273 K are achieved. Furthermore, such polymers display excellent iodine vapor uptake of up to 202 wt% and shows remarkable capability as iodine sorbent in solution. These results are significant for constructing accessible aromatic networks with promoted microporosity targeting for environmental challenges.