Abstract: Homocoupling of aryl halides (Ullmann-type reaction) promoted by a Pd-poly(N-vinyl-2-pyrrolidone)/MCM-48 (Pd–PVP/MCM-48) nanocomposite catalyst is described. In situ polymerization method was employed to prepare composite poly(N-vinyl-2-pyrrolidone)/MCM-48 (PVP/MCM-48) which was used as a support for palladium nanoparticles obtained by reducing Pd(OAc)2 with hydrazine hydrate. FT-IR, XPS, XRD, UV–Vis, SEM, and BET techniques were used to study the chemical and physical properties of the catalyst. The catalytic performance of this heterogeneous catalyst was specified for Ullmann-type reaction between aryl halies in DMF. The catalyst was good with regard to its stability and it can be reused up to six times without significant loss of its activity.