This paper presents a complementary analytical approach to characterize vegetable tanning materials in historic leathers. It is described the application of two molecular spectroscopic techniques, ATR-FTIR and UV-Vis, and three specific chemical tests to analyze tannins present in leathers. Acid butanol, nitrous acid and rhodamine colorimetric test, evaluated both visually and spectrophotometrically, were used to identify condensed tannins, ellagitannins and gallotannins, respectively. Ten samples of commercial, or laboratory prepared, vegetables tannins and seven new vegetable tanned leathers were also analyzed and obtained results were used for comparison. The complete analytical procedure was performed, in a semi-micro-destructive scale, using fibres collected from leather. Analysis of ATR-FTIR and UV spectra of commercial and laboratory prepared vegetable tannins allowed the establishment of the characteristic bands of condensed and hydrolysable tannins and, more specifically, gallotannins. These data were used to confirm the type of vegetable tanning agents used in new lather extracts. The same approach was used in cultural heritage leathers, supported by the colorimetric tests, since protein degradation products were co-extracted in aged leathers and interfered in IR spectra.