In the present study, polymer nanocomposite layers for sensing applications are characterized by means of an optical method based on white light interferometry. The study focuses on poly (hydroxy ethyl methacrylate) (PHEMA) and on nanocomposite Carbon black (CB)/PHEMA layers commonly used in chemical sensor technology for volatile organic compounds (VOCs) detection. The interferometric spectra of these two different materials, recorded during analyte exposure, are analyzed in terms of film expansion. Comparison between PHEMA and PHEMA/CB layer shows that the nanocomposite undergoes a more pronounced swelling process. In order to achieve a better comprehension of the sensing mechanism and to improve the sensor performances, the variations of the electrical signal of a nanocomposite-based chemiresistor in presence of VOCs are examined and compared to the optical behaviour.