Eight new substituted phenylamino and diaminoglyoximes; N-(3-methylphenyl)aminoglyoxime (MPAGH2), N-(2,6-dimethylphenyl)amino-glyoxime (DMPAGH2), N-(2-chloro-4-methylphenyl)aminoglyoxime (CMPAGH2), N-(2,4-dichlorophenyl)aminoglyoxime (DCPAGH2), N,N’-bis-(3-methylphenyl)diaminoglyoxime (BMPAGH2), N,N’-bis(2,6-dimethyl-phenyl)diaminoglyoxime (BDMPAGH2), N,N’-bis-(2-chloro-4-methyl-phenyl)diaminoglyoxime (BCMPAGH2), and N,N’-bis(2,4-dichlorophenyl)-diaminoglyoxime (BDCPAGH2) have been synthesized by the reactions of anti-chloroglyoxime and dichloroglyoxime with substituted aromatic amines in absolute ethanol. All these dioximes are in the anti- form according to IR and 1H NMR spectral data. The Ni(II), Cu(II) and Co(II) complexes of eight vic-dioximes have been prepared and their structures have been determined by using IR and UV-VIS spectral data and elemental analyses. © 1995, Taylor & Francis Group, LLC. All rights reserved.