Supported lipid structures and human cells (human dermal derived keratinocyte, HaCaT) were investigated using tip-enhanced Raman spectroscopy (TERS) to use the high spatial resolution capabilities of TERS, which is assumed to be less than 10 nm, to determine specific components on the cell surface. As lipids are a main component of cellular membranes, the correlation of spectral properties of pure lipidswith respect to the complex biological sample was investigated. Induced by dynamic structural changes aswell as nanoscale effects, a particular spectral feature of the lipid TERS spectra is found to vary, and a similar spectral deviation appears among the TERS spectra measured on the cell. Modifications of the cell surface alone cannot cause such behaviour. In contrast to soft lipid agglomerates, the cells were fixed and therefore hampered for intrinsic structural changes. Hence, themain contribution for the cell TERS spectra variation results from nanoscale effects, determined by different spectral characteristics compared to conventional Raman spectroscopy. The present results demonstrate the capability of TERS to provide a detailed and fast insight into the composition of the cell surface, even allowing the detection of single components.