Two imine-linked polymer organic frameworks (POFs) with different geometries (C3v-POF and Th-POF) and mesoporous properties were prepared and proved to be catalyst supports. Due to the greater ability of Th-POF to coordinate metals, Cu- and Ir-coordinated Th-POFs were tested as catalysts. Both act as truly heterogeneous catalysts towards cyclopropanation and hydrogenation of alkenes, respectively. The high surface area and easy accessibility to the catalytic sites make these materials very efficient for heterogeneous catalysis. The stability of the coordinated complexes and the porous frameworks allows several reuses with only a minor loss in catalytic activity.