The isolated‐pentagon rule (IPR) is a determining structural feature accounting for hollow fullerene stabilization and properties related to Cn (n ≥ 60) cages. The recent characterization of an unprecedented non‐IPR hydrofullerene, C2v‐C66H4, bearing two heptagons with adjacent fused‐pentagons motif, largely dismiss this feature. Herein, employing DFT calculations, we explore the 13C‐NMR pattern and aromatic behavior of C2v‐C66H4.