An active and recyclable supported Ni catalyst was developed by thermally decomposing nickel tetracarbonyl to highly dispersive nickel nanoparticles onto treated zeolite 5A (TZ5A) impregnated with trifluoromethanesulfonic acid (TFMSA). Oxybis(methylene)dibenzene (OBMDB) and benzyloxybenzene (BOB) were used as lignin-related model compounds (LRMCs) to evaluate Ni-13%-TEMSA/TZ5A activity for the catalytic hydroconversion (CHC) of the LRMCs. The results show that Ni13%-TFMSA/TZ5A effectively induces the formation and transfer of H+ and biatomic active hydrogen, and thereby catalyzes the CHC of OBMDB and BOB to afford cyclohexane under mild conditions. The CHC includes the cleavage of C-O and C-C bridged bonds, the hydrogenation of benzene ring, and dehydroxygenation of the resulting phenylmethanol and cyclohexanol. Ni-13%-TFMSA/TZ5A can be easily separated and still active for the CHC after 3-times recycle.