Methods and systems for performing spectroscopic measurements of asymmetric features of semiconductor structures are presented herein. In one aspect, measurements are performed at two or more azimuth angles to ensure sensitivity to an arbitrarily oriented asymmetric feature. Spectra associated with one or more off-diagonal Mueller matrix elements sensitive to asymmetry are integrated over wavelength to determine one or more spectral response metrics. In some embodiments, the integration is performed over one or more wavelength sub-regions selected to increase signal to noise ratio. Values of parameters characterizing an asymmetric feature are determined based on the spectral response metrics and critical dimension parameters measured by traditional spectral matching based techniques.