The reactions of triphenylantimony or trimethylantimony with tert-butyl hydroperoxide in the presence of acetone oxime, acetophenone oxime, cyclohexanone oxime, or benzaldehyde oxime afforded monomeric triorganoantimony oximates Ph3Sb(ON=CMe2)(2), Ph3Sb(ON=CMePh)(2), Ph3Sb[ON=C(CH2)(5)](2), Ph3Sb(ON=CHPh)(2), and Me3Sb(ON=CMe2)(2) in 87-96% yields. X-ray diffraction analysis demonstrated that Ph3Sb(ON=CMe2)(2) and Ph3Sb(ON=CHPh)(2) have trigonal-bipyramidal structures, An analogous reaction with dimethylglyoxime gave rise to polymeric triphenylantimony dioximate in 96% yield. The reaction with butane-2,3-dione monoxime yielded chelate cyclic bis(triphenylantimony) oxides.