Refined design of sustainable sorbent demands to tackle the strong dependence for additional mesoporous support and low utilization in hot coal gas desulfurization. Unlike the well-established preparation of loading sorbents supported on zeolites, a vacuum-assisted self-assemble strategy tapping into the ordered channels of walnut wood is proposed to facilely fabricate three-dimensional (3D) (a%Ce–Mn)yAl2−yOx desulfurizers with anisotropy which provides a desirable macroporosity for rapid diffusion of H2S. Benefiting from the inherent straight channle in micron scale, the obtained (8%Ce–Mn)1.5Al0.5Ox presents the highest breakthrough sulfur capacity (289.79 mg g−1) and effective utilization (88.42%) at 700 °C. The favorable rapid diffusion of gases in micro/macropores improves greatly the H2O-resistance and anti-interference ability of 3D (8%Ce–Mn)1.5Al0.5Ox for high steam and concentration of reducing gas. The fast mass transport in sulfidation reaction at 700 °C is described perfectly by the improved deactivation kinetics model. This study opens a novel design of the ideal 3D desulfurizers with micron porosity inherited from hierarchical architecture of walnut wood for industrialization utilization in the near future.