This work focused on the synthesis of a catalyst based on layered double hydroxides with a molar cation concentration Ni/Cu/Fe/Mg/Al of 30/5/5/40/20 and its performance in the steam reforming of toluene as a model compound of biomass tar. Its performance at different temperatures (500, 600, 700, 800, and 900 °C) and steam/carbon molar ratios (S/C ratios) (1, 2, 4, 6, 8) was studied. The contact time used was 0.32 g h mol−1. The catalyst obtained allowed us to reach 98–99.87% gas conversion of toluene with a low carbon deposition on catalyst surface (1.4 wt %) at 800 °C and S/C = 4. In addition, conversions in the range of 600–700 °C were higher than 80% and 90%, respectively, and the type of carbon deposited on the catalyst was found to be filamentous, which did not significantly reduce the performance of the catalyst.