A heterogeneous nickel catalyst for the selective hydrogenolysis of aryl ethers to arenes and alcohols generated without an added dative ligand is described. The catalyst is formed in situ from the well-defined soluble nickel precursor Ni(COD)(2) or Ni(CH2TMS)(2)(TMEDA) in the presence of a base additive, such as BuONa. The catalyst selectively cleaves C-Ar-O bonds in aryl ether models of lignin without hydrogenation of aromatic rings, and it operates at loadings down to 0.25 mol % at 1 bar of H-2 pressure. The selectivity of this catalyst for electronically varied aryl ethers differs from that of the homogeneous catalyst reported previously, implying that the two catalysts are distinct from each other.