A method and system are presented for use in measuring one or more characteristics of patterned structures. The method comprises: providing measured data comprising data indicative of at least one Raman spectrum obtained from a patterned structure under measurements using at least one selected optical measurement scheme each with a predetermined configuration of at least one of illuminating and collected light conditions corresponding to the characteristic(s) to be measured; processing the measured data, and determining, for each of the at least one Raman spectrum, a distribution of Raman-contribution efficiency (RCE) within at least a part of the structure under measurements, being dependent on characteristics of the structure and the predetermined configuration of the at least one of illuminating and collected light conditions in the respective optical measurement scheme; analyzing the distribution of Raman-contribution efficiency and determining the characteristic(s) of the structure.