The control over microstructure in block copolymer thin films using external electric fields has become an interesting research topic. In this article, the effect of nanoparticle on the microdomain alignments in block copolymer (polystyrene-b-poly(2-vinylpyridine)/nanoparticle (Au) thin films under electric fields has been examined with transmission electron microscopy. The homogeneous dispersion of Au nanoparticles into the block copolymer matrix was achieved by surface modification of nanoparticles with compatible ligands. Compared with the phenomenon seen in the pristine block copolymer thin films, a peculiar alignment behavior was observed in the block copolymer/nanoparticle hybrid thin films under electric fields. In addition, the different pathways observed in the pristine and nanoparticle incorporated block copolymer thin films were also monitored as a function of exposure time. This work can provide the fundamental information for understanding microdomain alignment in block copolymer/nanoparticle thin films under external electric fields.