To investigate the polymer sequence and conformations at the single-molecule level, we employed ESD-STM. This advanced methodology, developed in recent years, enables the imaging of polymeric assemblies with sub-molecular resolution while avoiding issues related to aggregation and high-mass limitations. Poly(PCT-T) was vacuum deposited by ESD on a Au(111) surface at sub-monolayer coverages and analyzed in ultrahigh vacuum by STM. The polymers are oriented face-on with respect to the substrate and appear as linear chains of alternating smaller, circular, and larger, rectangular features that are identified as thiophene and PCT units, respectively (Figure ). In low molecular density areas of the sample, the polymers adsorb preferentially in the face-centered cubic (fcc) regions of the Au(111) herringbone reconstruction (Figure ), and follow its templating pattern, avoiding interacting with one another (Figure and, for a larger scale, Figure ). The potential energy barriers between different areas of the herringbone reconstruction act as an adsorption well to confine the polymers, that would otherwise be quite mobile under the STM tip (see for example Figure for a comparison of more/less constrained polymers). The polymers have the conformational flexibility to form bends to accommodate for the templating effect of the substrate but remain generally elongated.