Duplex microstructure of zirconia and alumina has been achieved via an organic-inorganic solution technique. Zirconium 2,4-pentanedionate, aluminum nitrate and polyethylene glycol were dissolved in ethyl alcohol without any precipitation. The organicinorganic precursor gels were turned to porous powders having volume expansion through explosive, exothermic reaction during drying process. The volume expansion was caused by abrupt decomposition of the organic groups in the gels during the vigorous exothermic reaction. The volume expanded, porous powders were crystallized and densified at 1500$^{circ}C$ for 1 h. At the optimum amount of the PEG polymer, the metal cations were well dispersed in the solution and a homogeneous polymeric network was formed. The polymer content also affected on the specific surface area of the synthesized powder and the grain size of the sintered composite.