Porous ceramics with a pore size of 60 μ m * 20 μ m was printed using the multi-materials printing method. The pore size was the smallest known ceramic pore size that can be directly printed, especially the pore height of 20 μ m in the longitudinal direction, which cannot be achieved by other ceramic additive manufacturing technologies. The feasibility of multi-materials 3D printing method was verified by sample printing and sintering. Further, the fiber-like effect in resin and ceramic material multi-materials printing was proposed, which enlarged the transverse pore size of the porous ceramics. This method can manufacture porous ceramics with a pore size of < 100 μ m and the pore distribution and structure can be designed. This can benefit product performance and expand application fields. In addition, the proposed printing method is expected to be applied in micro-chemical industries to manufacture ceramic mixers, dispersers, reactors, heat exchangers, ceramic microfluidic chips, and micro-ceramic scaffolds.