Copyright © 2020 American Chemical Society. We studied the alignment changes of polymer-capped gold nanorods (GNRs@PS) under an applied electric field by visible-near-infrared absorption and small-angle X-ray scattering (SAXS) measurements. Monodispersed GNRs with an aspect ratio of 4.0 were produced by the seed-mediated growth method using cetyltrimethylammonium bromide and sodium oleate binary surfactants. We investigated the phase transition between the ordered structure of GNRs@PS induced by the external electric field. At appropriate field strengths (>3 V/μm), the SAXS profiles of GNRs@PS showed a smectic ordered structure. Increasing the electric field strength densified the ordered structure and greatly increased the Raman signals (the 298 and 445 cm-1 bands) of the carbon tetrachloride (solvent) between the GNRs@PS. The insights gained are potentially applicable to catalysts, future displays, optical filters, and data storage devices. ©