By a novel freeze-gelcasting technique, ceramic bodies with unidirectional ordered and gradient porous structures were fabricated, using tert-butyl alcohol (TBA)/acrylamide (AM)/alumina (Al2O3) slurries. TBA, which can freeze below 25 °C and volatilize rapidly above 30 °C, was used as a template for forming pores. The porous structures could be controlled by the temperature conditions, resulting in special unidirectional and gradient porous structures over a long range of several millimeters. At the same time, gelation of AM was successfully introduced in this process, and played an important role in strengthening the green bodies (with compression strength over 10 MPa). Sintered Al2O3 with a high porosity showed high compression mechanical properties, which contributed to the high density of ceramic walls. This technique combines the two processes of cold freezing and thermal gelation in one procedure, and is considered to be potentially useful in many applications.