The study reports on the differences in hair microstructure of healthy people and patients with cancer. The research has experimentally proved that hair of healthy people has a dense structure with a prominent external layer. In contrast, the hair of cancer patients has a destroyed external layer that is partially absent due to the presence of ulcers. Hair structure defects relate to biochemical changes: cancer presence leads to the increased ratio between oxygen and nitrogen, primarily on account of the decreased nitrogen concentration and, consequently, the decreased peptide concentration. Peptides composition in hair structure was also investigated by fluorimetry. The spectra of fluorescence excitation have several maxima such as at 295, 350 nm. For cancer patients, the spectrum has a huge maximum at 295 nm, while the spectrum for healthy volunteers has a small maximum at the wavelength and is shifting toward shorter wavelengths. We assume that the peak at 350 nm is primarily defined by the elastin contained in hair. The maximum at 295 nm is connected with the presence of tryptophan-containing peptides presence, such as keratin extracted from the Henley layer with keratinized cells. The obtained results can be used to improve optical techniques of biomedical diagnostics of cancer diseases.