Zr(OPri)4∙(PriOH) reacts with N-phenylsalicylideneimine in anhydrous benzene in 1 : 2 molar ratio to afford [Zr{O(C6H4)CH=NPh}2{OPri}2] (1). Further reactions of1with various glycols yield heteroleptic complexes of the type [Zr{O(C6H4)CH=NPh}2{O-G-O}] [where-G-= (CH2)2(2), (CH2CHCH3) (3), (CH3CHCHCH3) (4), (CH2CHC2H5) (5), (CH2)3(6), (CH2CH2CHCH3) (7), and (CH2)6(8)]. All new derivatives have been characterized by elemental analyses, FTIR and NMR (1H and13C{1H}) studies. FAB mass spectra of1and7revealed the monomeric nature of these complexes. Complete hydrolyses and low temperature transformations of1and7using sol-gel technique formed tetragonal phase of ZrO2at 700 °C, whereas transformation of tetragonal to monoclinic phase occurred at 900 ° C. SEM observations of these samples indicate formation of agglomerates of nanocrystalline zirconia (Scherer analysis).