The main topic of this paper is the study of polyisoprene-multi wall carbon nanotubes (PiMWCNT) composite’s electrical conductivity and volatile organic compound sensing properties with respect to type of multi wall carbon nanotubes used. Electrical percolation parameters like percolation threshold and critical exponent of produced composites are determined and analyzed. PiMWCNT composites exhibit a promising sensitivity to the presence of volatile organic compounds. Therefore the composite’s sensing mechanism of volatile organic compounds are analyzed in more detail by applying an original measuring technique which enables simultaneous measurement of an electrical resistance, mass and length change measurement of the sample in the presence and subsequent absence of a vapour. Measurement results enabled the evaluation of both vapour diffusion behavior in the composite and electrical resistance change mechanism.