Three-dimensional　ordered　macroporous　(3DOM)　zirconia　(ZrO2)　with　high　surface　area　and　ordered　interconnected　network　structure　can　be　applied　to　the　solar　cell,　lithium　battery　and　catalytic　process.　In　this　work,　3DOM　ZrO2　was　prepared　via　the　infiltration　of　ZrOCl2　·　8H2O　solution　into　the　polystyrene　(PS)　colloidal　crystal　template　and　subsequent　heating　treatment.　The　characteristics　of　wall　of　ordered　macrospores　are　closely　related　to　application　performance　of　3DOM　ZrO2.　The　characteristics　of　pore　wall　of　3DOM　ZrO2,　such　as　the　microscopic　structure　and　chemical　composition,　were　investigated　by　scanning　electron　microscopy,　transmission　electron　microscopy,　energy　dispersive　spectrometry　and　infrared　spectroscopy,　respectively.　Moreover,　the　porous　structure　of　3DOM　can　be　tuned　via　changing　both　of　heating　temperature　and　size　of　PS　spheres.　The　monoclinic　3DOM　ZrO2　with　-C-O　groups　was　obtained　when　calcinated　in　the　temperature　range　from　450　to　550°C.