With a highly localized plasmonic field, tip-enhanced Raman spectroscopy (TERS) images have reached atomic-scale resolution, providing an optical means to explore the structure of a single molecule. We have applied the recently developed theoretical method to simulate the TERS images of trans and cis azobenzene as well as its derivatives on Au(111). Our theoretical results reveal that when the first excited state is resonantly excited, TERS images from a highly confined plasmonic field can effectively distinguish the isomer configurations of the adsorbates. The decay of the plasmonic field along the surface normal can be further used to distinguish different nonplanar cis configurations. Moreover, subtle characteristics of different molecular configurations can also be identified from the TERS images of other resonant excited states with a super-high confined plasmonic field. These findings serve as good references for future TERS experiments on molecular isomers.