A new type of polymer-layered double hydroxide nanocomposite bearing thiazole moieties was used to support CuI nanoparticles (NPs) as a heterogeneous catalyst for the synthesis of bis-N-arylsulfonamides. The prepared nanostructured catalyst (LDH@MPS-GMA-TZ-CuI) showed high catalytic activity, as well as excellent recyclability for the preparation of bis-N-arylsulfonamides via chemoselective reaction of 1,3-disulfonyl chloride and nitroarenes. The superior catalytic activity of the LDH@MPS-GMA-TZ-CuI is related to the high loading of CuI NPs and favorable surface properties.