A quaternary phosphonium and tertiary phosphorus functionalized microporous polymer was obtained via nickel(0)-catalyzed Yamamoto-type cross-coupling reaction. The integration ratio of signals (quaternary phosphonium to tertiary phosphorus atoms) was close to 3:2. The polymer networks were stable toward water, base, and acid, and indeed no change in surface area was observed even after the material was treated with 10 M HCl. The pore size distribution calculated by the Horvath-Kawazoe method indicated the presence of micropores with a mean width of about 0.7 and 1.4 nm. Their apparent BET specific surface areas can be tuned (from 650 to 980 m(2) g(-1)) by changing the counteranions (Br- to F-). It displays high intrinsic catalytic activity for the reaction between epoxide and CO2 (yield: 98%, 1 atm). Pd nanopartides supported on the polymer networks were also prepared, which exhibits high catalytic activity for cross-coupling reaction between 1-chlorobenzene and phenylboronic acid (yield: >95.8%).