New functionalized porous polyimides (PPIs-NO₂, PPIs-NH₂, and PPIs-NPy) were synthesized and characterized and the PPI-NPy materials were applied as supports to obtain heterogenized palladium-complexes (PPI-NPy-Pd). The PPI-NPy-Pd hybrid materials have behaved as very efficient heterogeneous catalysts in the Suzuki coupling reaction in water, affording the corresponding cross-coupling products in excellent yields. Furthermore, the catalysts have shown excellent chemical and thermal stability and good recyclability. No evidence of the leaching of Pd from the catalyst during the course of reaction was observed, suggesting true heterogeneity in our catalytic systems.