Some historical parchments belong to the cultural heritage of humankind and possess invaluable historical significance. Therefore, development of simple and reliable methods for parchment characterization and animal species identification is of importance. Multiphoton electron extraction spectroscopy (MEES) is a new analytical method for characterization of surfaces, and this is its first application to biomaterials in general and to parchments in particular. When comparing MEES of various parchments, it was found that the spectral intensity of historical parchments was significantly higher, and the main peak was broader than for the modern and artificially aged specimens. Gaussian fitting of the spectra indicated the presence of six peaks for modern and historical samples at nearly the same positions. Significant spectral differences between historical and modern samples were clearly observed. Animal species identification (calf, sheep and goat) was also possible, based on MEES analysis of modern parchments (grain side). Correlations to the electrical conductivity of the samples were also studied.