While surface-enhanced Raman scattering (SERS) is an established technique to significantly enhance the Raman signal from samples bound to metal surfaces, a quantitative interpretation is very difficult because of the rough and arbitrary nature of the substrate. A distinction between concentration and enhancement effects is virtually impossible. Tip-enhanced Raman scattering (TERS), a scattering type of near-field optical microscopy technique, circumvents the problem of random enhancement by concentrating the roughness to only a small region directly at the apex of a scanning probe tip. In this paper, TERS spectra of DNA pyrimidine bases have been collected and compared with standard SERS and Raman measurements of the nucleotides and the pure bases. The results are discussed in terms of electromagnetic and chemical effects of the SERS enhancement of the TERS probes.