A sensor system employs a thermo-electrically cooled surface enhanced Raman (SERS) structure that is positioned in a sample chamber. Gas or vapor that may contain an analyte of interest is introduced into the sample chamber so that the analyte may come into contact with the SERS structure. The SERS structure may be cooled to facilitate condensation of selected analytes onto the SERS structure. When in contact with each other, the analyte and SERS structure may be optically stimulated by an optical excitation signal to produce a unique spectral response that may be detected by a spectroanalysis system. The spectral response then may be correlated to a specific analyte, i.e., identified.