Novel nickel catalysts, prepared in situ by oxidative: addition of alpha -nitroketones to nickel(O) complexes, in the presence of a phophine ancillary ligand and activated by organoaluminium co-catalysts were investigated in propylene oligomerization with the aim to selectively obtain 2,3-dimethylbutenes (DMB). In particular, the effect of the nature of the alpha -nitroketonate ligand as well as of the basicity and bulkiness of the phosphine on catalyst performances were studied. Finally, the influence of the type of organoaluminium co-catalyst and reaction temperature were examined. In particular, when the Ni(cod)(2)/tricyclohexylphosphine (PCy3)/alpha -nitroacetophenone (naph)/methylalumoxane (MAO) catalytic system was employed, the highest up to now reported regioselectivity within C-6 cut (>90%) was achieved. Moreover, the use of balanced mixtures of MAO and Et2AlCl allowed to optimize the catalyst performances up to an overall yield to DMB of almost 70%, a significant productivity being also achieved (TOF = 4500 h(-1)).