Complexation of a rigid multi-pyridine ligand bis(2-pyridyl)-1,8-naphthyridine (bpnp) with [Cu₂(TFA)₄] (TFA = trifluoroacetate) resulted in the formation of a dinuclear copper(II) complex, namely [Cu₂(bpnp)(μ-OH)(TFA)₃] (1). This complex has been characterized by X-ray crystallographic, spectroscopic and elemental analyses. Complex 1 is an efficient catalyst for the oxidative coupling of various 2,6-disubstituted phenols with molecular oxygen. Yields and selectivity depend on the reaction conditions employed, the best results being obtained in isopropanol or dioxane at 90 °C with yields of >99%. Mechanistic pathway of the catalysis is discussed.