Tip-enhanced Raman spectroscopy revealed the nanoscale chemical properties of organic molecules encapsulated in single walled carbon nanotubes (SWNTsanalysis focuses is more on structural information, such as intermolecular interactions, molecular orientations, and symmetry distortions of each species. Moreover, vibrational spectroscopy can be used for identifying molecular species, which is not possible by TEM. Therefore, Raman spectroscopy is a powerful tool for studying the chemical composition of matter. Conventional confocal Raman spectroscopy techniques are limited to sub wavelength spatial resolution, and localized vibrational features of molecules encapsulated in SWNTs have not been resolved so far. This limitation has been overcome by the development of tip-enhanced Raman spectroscopy (TERS) [8][9][10][11][12][13][14][15][16]. By introducing a sharp metal tip to the focus of a laser beam, we were able to localize Raman excitation to an area of 30 nm 2 [17][18][19]. This technique has recently enabled the molecular nanoimaging of a single carbon nanotube [20] and double-stranded DNA network structures [21].