Macroporous yttria-stablized tetragonal zirconia has been synthesized combining the sol–gel with Pechini method. Polyacetylacetonatozirconium (PAZ) served as the zirconium precursor while polyvinyl alcohol (PVA) was used as pore template. The thermal behaviors of xerogel and porous zirconia were determined by thermogravimetric/differential thermal analysis (TG/DTA). FT-IR, FE-SEM, and XRD analysis indicated that the organic components of xerogel have been completely removed and porous zirconia was formed after annealing at 600°C for 2h in air. The skeleton is composed of zirconia particles with diameter of about 60nm and the pore diameter is about 68nm. The surface area and pore volume of the bulk macroporous yttria-stablized tetragonal zirconia are 9.4m2/g and 0.016cm3/g, respectively, evaluated from nitrogen adsorption/desorption measurements.