A new concept of the formation of charge transfer (CT) complexes between an intrinsically electron-donating conjugated microporous polymer and a small molecule acceptor is reported. Spirobifluorene-based mesoporous organic polymers with high porosity and Brunauer–Emmett–Teller surface area are synthesized by the Suzuki-coupling reaction of spirobifluorene and pyrene monomers. The simple doping of the synthesized mesoporous, electron-rich, conjugated polymer with 7,7,8,8-tetracyanoquinodimethane as an acceptor leads to efficient CT complexation in the electron-donating mesoporous spaces. This results in a high-speed synthesis (within 5 s), thermally stable compound (up to about 200 °C), and good control of the concentration of donor–acceptor pairs in the CT complex.