Treatment of the acetonitrile complex mer-[RhCl₃(MeCN)₃] with cyclopentanone oxime (C₄H₈)CNOH resulted in the formation of two rhodium(III) products that contain newly formed chelated iminoacyl ligands, i.e. [RhCl₃{NHC(Me)ONC(C₄H₈)}{HONC(C₄H₈)}] and [RhCl₂{NHC(Me)ONC(C₄H₈)}₂]Cl·1.5H₂O. Only one iminoacylated product, i.e. the rhodium(III) complex [RhCl₂{NHC(Ph)ONC(C₄H₈)}₂]Cl·H₂O·EtOH, has been isolated in the reaction between the oxime and the benzonitrile complex mer-[RhCl₃(PhCN)₃] in ethanol. A formally reverse reaction between [RhCl₃{HONC(C₄H₈)}₃], prepared on treatment of RhCl₃·4H₂O with the oxime in EtOH, and free organonitrile has also been carried out. All products were characterized by elemental analyses (C, H, N, Cl, Rh), FAB⁺-MS, IR, ¹H and ¹³C-{¹H} NMR spectroscopies. X-Ray single-crystal analyses were performed for [RhCl₃{NHC(Me)ONC(C₄H₈)}{HONC(C₄H₈)}], [RhCl₂{NHC(Me)ONC(C₄H₈)}₂]Cl·1.5H₂O, [RhCl₂{NHC(Ph)ONC(C₄H₈)}₂]Cl·H₂O·2EtOH and mer-[RhCl₃{HONC(C₄H₈)}₃].