A porous cross‐linked poly (ethyleneamine)‐polysulfonamide (PEA‐PSA) as a novel organic support system is synthesized in the presence of silica template by nanocasting technique. The paper demonstrates immobilization of CuI nanoparticles inside the pores (PEA‐PSA@CuI) for the facile recovery and recycling of these nanoparticles. The presence of porous PEA‐PSA and PEA‐PSA@CuI nanocomposites was confirmed using FT‐IR spectroscopy, FE‐SEM, EDX, TGA, XRD, TEM, BET, XPS, WDX, 1H NMR, and ICP‐OES techniques. The PEA‐PSA@CuI along with Ag(I)/K2S2O8 was implemented as a reusable cooperative catalyst‐oxidant system in the N‐arylation of p‐toluenesulfonamide with substituted carboxylic acids in mild condition. So, the novel decarboxylative cross‐coupling catalyzed by copper and silver has been developed. Aromatic, secondary and tertiary aliphatic acids underwent high efficient decarboxylative processes with p‐toluenesulfonamide to afford the corresponding products. This method provides a practical approach for the flexible synthesis of sulfonamides from the readily affordable substrates. The catalyst is highly reusable and efficient, especially in terms of time and yield of the desired product.