The chemo-electrical properties of chitosan-carbon nanotubes (Chit-CNT) Conductive bio-Polymer nano-Composites (CPC) transducers processed by spray layer-by-layer (LbL) technique have been investigated. Results show that unlike most synthetic polymer matrices, chitosan provides the transducer with high sensitivity towards not only polar vapours like water and methanol but also to a lesser extent toluene. Quantitative responses are obtained, well fitted with the Langmuir-Henry-Clustering (LHC) model allowing to link electrical signal to vapour content. Chit-CNT transducers selectivity was also correlated with an exponential law to the inverse of Flory-Huggins interaction parameter chi(12). These properties make Chit-CNT a good transducer to be implemented in an e-nose. Additionally, the observation by atomic force microscopy (AFM) of Chit-CNT morphology suggests a chemical nano-switching mechanism promoting tunnelling conduction and originating macroscopic vapour sensing.