A collection of five related 2-(arylimino)pyridines, 2-{(2,6-(CH(C6H4-p-F)2)2-4- RC6H2)N=CMe}C5H4N, each ortho-substituted with 4,4′-difluorobenzhydryl groups but distinct in the electronic properties of the para-R substituent (R = Me L1, Et L2, i-Pr L3, F L4, OCF3 L5), were prepared and combined with (DME)NiBr2 to form their corresponding LNiBr2 complexes, Ni1–Ni5, in high yields. All the complexes were characterized by FT-IR, 19F NMR spectroscopy and elemental analysis, while Ni5 was additionally the subject of an X-ray determination, revealing a bromide-bridged dimer. The molecular structure of bis-ligated (L4)2NiBr2 (Ni4’) was also determined, the result of ligand reorganization having occurred during attempted crystallization of Ni4. On activation with either EtAlCl2 or MMAO, Ni1–Ni5 exhibited high catalytic activities (up to 4.28 × 106 g of PE (mol of Ni)−1 h−1 using EtAlCl2) and produced highly branched polyethylene exhibiting low molecular weight (Mw range: 2.50–6.18 kg·mol−1) and narrow dispersity (Mw/Mn range: 2.21–2.90). Notably, it was found that the type of para-R group impacted on catalytic performance with Ni5 > Ni4 > Ni3 > Ni1 > Ni2 for both co-catalysts, underlining the positive influence of electron withdrawing substituents. Analysis of the structural composition of the polyethylene by 1H and 13C NMR spectroscopy revealed the existence of vinyl-end groups (–CH=CH2) and high levels of internal unsaturation (–CH=CH–) (ratio of vinylene to vinyl, range: 3.1:1–10.3:1) along with various types of branch (Me, Et, Pr, Bu, 1,4-paired Me, 1,6-paired Me and LCBs). Furthermore, reaction temperature was shown to greatly affect the end group type, branching density, molecular weight and in turn the melting points of the resulting polyethylenes.