AbstractThe gold nanowire arrays with different diameter and length were successfully prepared in etched ion‐track template assisted with electrochemical deposition method and the nanowire's crystal structure and morphology were characterized by transmission electron spectroscopy (TEM) and scanning electron spectroscopy (SEM). The X‐ray photoelectron spectroscopy (XPS) was used to analyse the electronic states of gold nanowire arrays embodied in the template. It was found that the 4f core level binding energy of gold nanowire shifted toward higher binding energy when comparing with bulk gold. The positive binding energy shift increased significantly with decreasing nanowire's length or diameter. The enhanced final‐state effect was considered to explain the 4f binding energy shift of gold nanowire arrays embodied in template finally. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)