Interesting results, presenting the use of different stibine ligands in amidocarbonylation of cyclohexene and l-pentene catalyzed by Co-2(CO)(8), not only enhance the activity of catalyst but also increases the selectivity in comparison to classical phosphinic ligands, have been reported. The stibine and phosphine ligands used were triphenylstibine (TPS), o- and p-tritolylstibine, (o-TTS, p-TTS) 2,4,6-trimesitylstibine (TMS), p-trifluorophenylstibine (p-TFPS), triphenylphosphine (TPP), o- and p-tritolylphosphine (o-TTP, p-TTP), respectively. All the reactions were carried out in a very mild syngas pressure (25 bar).