Several new symmetrical and unsymmetrical amides of the types (Rf)3Sb(NR2)2 and (Rf)3RSb(NR2) (where, Rf = C6F5; R = C6H5 and NR2 = have been prepared by the metathesis of (Rf)3SbCl2 or (Rf)2RSbCl with the appropriate metal salts of the organic ligands. The amide derivatives were also obtained by the interaction of pentafluorophenylantimony(V) chloride with organic ligand(1:1 &1:2 molar ratio) using triethylamine as hydrogen chloride acceptor. The newly synthesized compounds have been characterized by conventional methods. A tentative trigonal bipyramidal structure is suggested for these compounds. The failure of reaction between (Rf)3Sb(NR)2 and CS2 even after prolonged refluxing may be attributed to the weak dipole nature of the CS2 and the presence of electron withdrawing group on antimony amide.