The electrical breakdown strength of TiO2 nanoparticle-filled low-density polyethylene (LDPE) nanocomposites was investigated. It was found that the surface water on the nanoparticles played a very important role in determining the breakdown strength. The breakdown strength at 63.2% cumulative failure probability (E0) for the composites filled with dried nanoscale TiO2 was similar to that of neat LDPE and 50% higher than that for the samples filled with as-received nanoscale TiO2. This increase was due to a better dispersion, a better interface, and a morphology change of the matrix. It was also found that surface modification of nanoscale TiO2 had a significant influence on the breakdown strength. N-(2-aminoethyl) 3-aminopropyl-trimethoxysilane (AEAPS)-coated TiO2-filled samples showed about 40% higher E0 than that of uncoated, as-received TiO2-filled samples. This was mainly due to enhanced electron scattering because of the presence of polar groups in AEAPS.