This paper investigates partial discharge (PD) characteristics of crosslinked polyethylene (XLPE) nanocomposites for unmodified, agglomerated, and Octylsilane-modified silica nanofillers (nano 1, 2, 3, 4, 5, 10 wt %) case. The surface modification of nanofiller helps to reduce the PD formation marginally. Octylsilane surface-modified XLPE/silica nano 3 wt % exhibits the lowest PD activity with highest discharge inception voltage and breakdown voltage. Also, the issue of change in the polymer structure due to the addition of nanofillers is reported here. The differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), fourier transform infrared (FTIR), and contact angle measurement study conducted suggests that the addition of nanosilica leads to the change in the melting point, thermal degradation temperature, heat of fusion, bonding structure and the contact angle of the polymer, respectively. These structural changes are explained with the supporting theory.