Organic isocyanide adsorbed on a noble metal nanostructure can be used as a platform for a volatile organic compound (VOC) sensor operating via surface-enhanced Raman scattering (SERS). This is possible since the NC stretching band of organic isocyanides such as 2,6-dimethylphenylisocyanide (2,6-DMPI) is very susceptible to the surface potential of Au onto which 2,6-DMPI is assembled. The surface potential of Au nanoparticles is even subject to change by VOCs, which can be easily monitored by the SERS of 2,6-DMPI. Thereby, under the flow of CCl(4) vapor at a partial pressure of 12.8 kPa, for instance, the NC stretching band is blue-shifted by up to 20 cm(-1) within 30 s, corresponding to a potential change of +0.56 V. Conversely, under the flow of butylamine at 12.8 kPa, the NC stretching band is red-shifted, instead of being blue-shifted, by as much as 12 cm(-1). At lower partial pressures, even a blue- or red-shift of 1 cm(-1) was reproducibly measured at a partial pressure of 125 mPa, corresponding to 6.5 ppm for CCl(4), suggesting that the present detection limit is superior to the results obtained via other techniques, especially those operating based on gold nanoparticles and aggregates.