The development of efficient Ni-based catalysts for steam reforming of biomass tar is crucial for the widespread application of biomass gasification. Multimetal high-entropy alloys (HEAs) have emerged as promising catalysts that can potentially replace conventional metallic materials in various applications. In this study, we investigate NiFeCoMnCu-HEA catalysts supported on the surface of wood carbon (WC) for highly efficient steam reforming of toluene, a model compound for biomass tar. The synergistic effect between Ni and the other four metals in the HEA composition inhibits coke formation during the reaction process, while the appropriate mole ratio of Ni: (Fe + Co + Mn + Cu) reduces the particle size of HEA nanoparticles. Furthermore, the unique structure of wood carbon, with its long, interconnected, yet distorted microchannels, enhances the dispersion of active sites and improves mass transfer efficiency. As a result, the NiFeCoMnCu-HEAs/WC catalyst exhibits outstanding catalytic activity, achieving over 95% toluene conversion for 48 h at 650 °C. This performance surpasses that of the compared catalysts prepared in this work, namely NiFeCoMn/WC (39%), NiFeCoCu/WC (31%), and NiFeCo/WC (20%), underscoring the significance of the HEA structure. The findings also offer valuable insights into enhancing the performance of other nanostructures in the steam reforming of biomass tar.