An optical measurement system for evaluating a sample has a motor-driven rotating mechanism coupled to an azimuthally rotatable measurement head, allowing the optics to rotate with respect to the sample. A polarimetric scatterometer, having optics directing a polarized illumination beam at non-normal incidence onto a periodic structure on a sample, can measure optical properties of the periodic structure. An E-O modulator in the illumination path can modulate the polarization. The head optics collect light reflected from the periodic structure and feed that light to a spectrometer for measurement. A beamsplitter in the collection path can ensure both S and P polarization from the sample are separately measured. The measurement head can be mounted for rotation of the plane of incidence to different azimuthal directions relative to the periodic structures. The instrument can be integrated within a wafer process tool in which wafers may be provided at arbitrary orientation.