4-Chloroacetylbiphenyl has been synthesized by Friedel-Crafts reaction between biphenyl and chloroacetyl chloride in the presence of AlCl3 catalyst. The nitrosation reaction of this compound gave 4-biphenylhydroxamyl chloride (HL). Subsequently, 4-biphenylchloroglyoxime (H2L) was prepared by the reaction of 4-biphenylhydroxamyl chloride and hydroxylamine hydrochloride. Then, six new substituted 4-biphenylaminoglyoximes (H2Lx) have been synthesized from 4-biphenylchloroglyoxime and the corresponding amines. A series of M(II)-dioxime complexes of the type [M(HLx)(2)] or [M(HLx)(2) (H2O)(2)] [M(II)=Co(II), Ni(II), Cu(II)] have been synthesized and characterized by FT-IR, H-1 NMR spectral studies, elemental analysis, AAS and magnetic susceptibility measurements.