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An approach towards incorporating varied degrees of steric profiles around the ligand’s backbone, which were envisaged to alter the catalytic paths leading to targeted 1-C₈/1-C₆ olefin products, were explored. Cr-pre-catalysts designed with PNP ligands comprising a fused aryl moiety were delivered at a relatively higher C₈ olefin selectivity (up to 74.6 wt% and C₈/C₆ of 3.4) when the N-connection to the aromatic unit was placed at the 2-position. A relatively higher C₆ olefin selectivity (up to 33.7 wt% and C₈/C₆ of 1.9) was achieved with the PNP unit anchored at the 1- or 6-position. Based on detailed catalytic studies, we confirm the fact that by introducing a controlled degree of bulkiness on the N-site through a judicious selection of the N-aryl moiety of different sizes, the selectivity of the targeted olefin product could be tuned in a rational manner.