Porous ceramics with complex pore structure were synthesized by a freeze-dry process. Freezing-in of a water-based ceramics slurry was done while controlling the growth direction of the ice. Sublimation marks of the ice were generated by drying under reduced pressure. Porous ceramics having a complex pore structure were obtained by sintering the green body: aligned macroscopic open pores contained micropores in their internal walls. The pore structure was substantially affected by the starting slurry concentration and sintering temperature. The pore formation mechanism is discussed in relation to these effects.