The optical sensing properties of nanometric polyimide films towards ethanol and methanol vapours have been investigated by surface plasmon resonance technique. To this purpose polyimide sensing layers have been deposited onto gold/glass substrates by glow-discharge-induced vapour deposition polymerization technique. The sensible layer shows reversible and stable responses to different concentrations of methanol and ethanol vapours. A linear dependence between the change in reflectivity and the vapours concentration is observed being the sensitivity to both vapours similar, however, the response is larger in presence of ethanol vapours. Numerical fitting routines on surface plasmon resonance curves indicate that optical changes are motivated by an absorption process of the analyte. This produces a detectable increase of the real refractive index and a swelling process in the polyimide layer.