High-energy ball milling was tested as a method for producing Ultra High Molecular Weight Polyethylene (UHMWPE)-based nanodielectrics containing 1 wt% and 5 wt% OctaIsoButylPOSS (OibPOSS). Qualitative and quantitative evaluations were used to explore the compatibility between OibPOSS and PE. Several ball milling variables were optimized in a bid to achieve UHMWPE/OibPOSS nanodielectrics. The morphology, as well as the thermal and the dielectric properties of the samples, were characterized by scanning electron microscopy, thermogravimetric analysis, broadband dielectric spectroscopy, and progressive-stress breakdown tests. The results showed that (i) ball milling was an effective method for producing UHMWPE/OibPOSS dielectric composites, but appeared ineffective in dispersing OibPOSS at the nanoscale, and (ii) the resulting UHMWPE/OibPOSS dielectric composites presented thermal and dielectric properties similar to those of neat UHMWPE.