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Biomimetic porous ceramics have great application potential in the petrochemical industry; their biomimetic porous structure is conducive to mass transfer, energy exchange and catalytic reactions. However, it is challenging to produce biomimetic porous ceramics with complex shapes using conventional processes. Herein, we demonstrate a novel structural bionic and 3D printing strategy and a pseudo-boehmite-based slurry for fabricating hierarchical alumina ceramic carriers with biomimetic vein structures. Tuneable hierarchical porosity from nm to mm scales, high specific surface area, and superior strength have been achieved by innovatively combining dehydroxylation and peptisation of pseudo-boehmite, direct ink writing (DIW), and post-sintering processes. The effects of post-sintering temperature and impregnation treatment on the crush strength, porosity, and specific surface area were systematically investigated. The optimised porous ceramics exhibited a crush strength of 54.453 ± 7.359 N/cm, specific surface area of 109.870 ± 0.143 m2/g, and porosity of 60.03 ± 2.72%. The catalytic test for dry reforming of methane was conducted on biomimetic catalysts loaded with nickel (Ni) and phosphorus (P). The biomimetic catalyst had a remarkable methane conversion of 41.27%, in addition to mass transfer and coke inhibition effects. Through the integrated biomimetic design of macro–micro structures, monolithic alumina catalyst carriers with biomimetic vein structures prepared by DIW can potentially be used more efficiently in industrial catalytic reactions. [ABSTRACT FROM AUTHOR]