Gold gratings were measured by spectroscopic ellipsometry in reflection mode and modeled by the finite element method to investigate the capabilities of optical dimensional metrology for plasmonic diffractive structures. The gratings were prepared by electron beam lithography using parameters determined by finite element simulations for significant variations of the amplitude ratio and phase shift of the polarized reflection coefficients to achieve high sensitivity for both the measurement of the grating dimensions and the sensing capabilities. The sensitivity largely depends on the values in the five-dimensional parameter space including the grating parameters such as the critical dimension, the period, and the thickness of the grating, as well as the measurement parameters comprising the wavelength and the angle of incidence. The best limit of detection values are in the picometer range for the critical dimension and the thickness of the overlayer, and ≈10–5 for the refractive index.