Abstract:zinc chlorideand aluminum chloride (AlCl3.6H2O, Aladdin, 97%) were chosen as zinc and aluminum precursors, a mixture of distilled water (H2O) and ethanol was used as the solvents. Propyleneoxide was used to immediate the gelation process, and poly(ethylene-oxide) was used as a phase-separation inducer. All the chemical reagents were used as received. Porous ZnAl2O4 spinel monolith has been successfully prepared via the sol–gel route accompanied by phase separation. The as-prepared samples were characterized by means of XRD, DTA, SEM and FTIR, the inpact of heat-treatment on the structure and phase transmition were discussed. The results show that phase separation can be induced by PEO, thus obtain a prous monoliths with a interesting pore structure with co-continuous solid skeletons and well-controlled pores. The as-prepared samples shows a phase of(ZnAl-LDHs, The ZnAl2O4 crystalline phase is obtained after the decomposition of –OH and carbonate anions during the heat treatment at 600 oC in air. The materials can be widely applied in many catalytic fileds in the future.