A 2D porous MOF, {[Cu(1,2,3-btc)(bpe)(H₂O)]·H₂O}_n (1), has been synthesized using a mixed linker system. The structural determination showed non-coordinated carboxylate groups decorating the pore surface. The desolvated MOF (1a) with pendant carboxylate groups was used as a template for the stabilization of Pd nps (2–3 nm) and the resulting composite Pd(0)@1a showed efficient catalytic activity for the Suzuki–Miyaura C–C coupling reaction.