AbstractPlasmonic nanostructures offer an enticing prospect in many applications, ranging from lasing to biosensing, due to their unrivaled light concentration beyond the diffraction limit. However, this promise is substantially undercut by the intrinsically high losses in metals. Here, an experimental ultra‐high‐Q plasmon resonance with a linewidth down to 2 nm (Q‐factor ≈ 350) and a resonance intensity of 51% in an ultrasmooth gold nanogroove array is reported. Such an experimental ultranarrow resonance arises from two key factors. First, a geometrical‐induced coupling between the Fabry–Pérot and Wood's anomaly modes significantly suppresses the groove array's radiative damping. Second, an ultrasmooth gold surface fabricated by template stripping minimizes its surface scattering and grain boundary scattering. Benefiting from this ultranarrow resonance, a figure of merit (FOM) of 284 and an FOM* of 617 in refraction index (RI) sensing under normally incident detection are demonstrated, the former of which is the record FOM in all reported broad‐RI‐range plasmonic RI sensors. The array is further demonstrated as a surface thickness sensor for detecting mercaptocarboxylic acids with the surface sensitivity of 0.18 nm/CH2, which suggests that the array is a promising platform for thickness detection of surface analytes and label‐free biomedical sensing.