Bis(diphenylphosphino)amine (PNP) ligands with different alkyl and cycloalkyl substituents attached to the N atom of the ligand backbone were synthesised and tested together with chromium as ethylene tetramerization catalysts. On activation with a methylaluminoxane-based activator, the catalysts displayed good activity and selectivity toward 1-octene and 1-hexene, with the best ligand systems containing cyclopentyl or cyclohexyl moieties. In addition, it was established that substitution at the 2 position of the cyclohexyl skeleton and, more importantly, an increase in steric bulk at that point, led to a drastic reduction of side product formation (i.e., methyl- and methylenecyclopentane). Interestingly, additional methyl substitution in the 6 position of the cyclohexyl ring changed the selectivity of the catalyst from predominantly tetramerization to a 1:1 mixture of 1-hexene and 1-octene. Structurally similar ligands, such as cyclohexylmethyl and cyclohexylethyl PNP, were also tested and were also found to yield efficient tetramerization catalysts. It was concluded that structural fine tuning of the N-alkyl moiety of the PNP ligand is essential for obtaining efficient tetramerization catalysts, with the best systems achieving combined selectivities as high as 88% (1-octene and 1-hexene) with exceptionally high activities exceeding 2,000,000 g/(g-Crh). (c) 2006 Elsevier Inc. All rights reserved.