Exfoliated polynorbornene (PNBN)/montmorillonite (MMT) nanocomposites were synthesized for the first time by the surface-initiated ring-opening metathesis polymerization. PNBN is one of the challenging materials in low dielectric films for packaging applications in electric-electronic industries. This is the first example of in situ polymerization of NBN within the catalyst intercalated montmorillonite layers using ROMP in different clay loading degrees. The Na-MMT clay was modified with a Quaternary ammonium salt containing ruthenium complex as a suitable catalyst and intercalant as well. Powder X-ray diffraction spectroscopy and transmission electron microscopy analysis indicated that the resultant nanocomposites exhibited exfoliated morphologies with homogeneous clay platelet distribution. Nanocomposite materials were obtained with high thermal degradation temperature and low dielectric constant when compared with pure PNBN. The dielectric constants decreased with the increase in the clay content.