Raman spectroscopy is a capable and prominent method for probing the relationship between structure, dynamics and function of biomolecules. However, the Raman scattering efficiency and therefore the sensitivity is rather poor. To overcome this drawback which does not allow investigating biomolecules at very low concentration levels, particular Raman-signal-enhancing techniques such as, for example, surface enhanced Raman scattering (SERS) have been developed and introduced. In SERS a rough metal surface is brought into close contact to a sample to experience electromagnetic and chemical enhancement factors up to 10 11 -10 14 . Consequently, rich chemical information with high sensitivity can be obtained, allowing, for instance, the rapid identification of bacteria by their SER spectra. [1][2][3] Quite a new technique, tip-enhanced Raman spectros-A C H T U N G T R E N N U N G copy (TERS), combines SERS with atomic force microscopy (AFM). Thus, detailed and sensitive spectral information can be obtained with a spatial resolution below the diffraction limit. [4] In TERS the enhancing SERS roughness is reduced to a sharp tip of less than 50 nm in diameter. This probe is used to record the surface features (AFM). Simultaneously, illumination with a laser beam excites confined localized surface plasmons that cause an enhanced Raman signal in a very small area. So far, this approach was only applied to pure substances such as CN À ions adsorbed at gold surfaces, [5] malachite green isothiocyanate, [6,7] benzenethiol, [8] rhodamine 6G, [9] DNA components [10] and single-walled carbon nanotubes. [11,12] Herein, we report to the best of our knowledge for the first time on TER spectra of complex biological systems, that is, bacterial cells. This marks a big step forward towards the investigation of bacterial surfaces without the need of labeling techniques. With the high spatial resolution and the structural information of the vibrational spectra obtained by TERS new insights in structure details, composition and arrangement of the individual