A well-defined heterogeneous palladium catalyst, supported on biomacromolecule, natural wool fibre, was found to be an effective catalyst for the C–C/C–N coupling of pyrimidin-2-yl sulfonates with arylboronic acids, terminal alkynes or anilines, giving the desired coupling products in good to high yields. The catalyst was characterized by XPS, IR, SEM and ICP. More importantly, the easy experimental handling catalyst is stable, shows negligible metal leaching, and can be reused for at least 10 successive runs. Undoubtedly, a wide scope of reactant, insensitive to the electron effects and the excellent coupling yields make these catalyst systems potentially useful in organic synthesis.