In summary, we developed the two new biplane-type NHC ligands BI*Ph and BIF*Ph based on a benzimidazolylidene core, whose lower wings are set as N-phenyl rings to reduce their steric hindrance on the first coordination sphere and whose upper wings are phenyl or pentafluorophenyl rings, respectively. The corresponding second-generation Grubbs-Hoveyda complexes Ru16 and Ru17 were generated and the effect of the introduction of the second decker of aromatic rings on their stereoelectronic properties, stability, and catalytic efficiency was evaluated, taking the monoplane-type, unsubstituted BIPh ligand as a reference. According to the nature of the aromatic rings, BI*Ph was shown to be more electron-donating than BIPh, while BIF*Ph is less donating. By computing the electrostatic potential surfaces for complexes Ru16opt and Ru17-opt, we have shown that complex Ru16-opt contains two electron-rich aromatics whereas complex Ru17-opt alternates electron-rich and electron-deficient aromatics. According to the polar/π Hunter and Sanders model, therefore, complex Ru17-opt displays a stronger electrostatic interaction between the stacked aromatic rings than its analogue Ru16-opt, leading to shorter ring centroid distances between the pentafluorophenyl and the N-phenyl rings (3.427 and 3.450 Å) in Ru17-opt compared to those between the phenyl and the N-phenyl rings (3.607 and 3.612 Å) in Ru16-opt.