Valonea is one of many well-known vegetable tannins used in tanning and retanning processes for leather making. Although it is used extensively in the leather industry, its main components and chemical structure are only gradually being identified. In order to investigate the chemical structure of valonea with novel techniques, MALDI-TOF (Matrix-Assisted Laser Desorption/Ionisation Time-of-Flight) and FTIR (Fourier Transform Infrared) Spectroscopy were used. The MALDI-TOF spectrum showed the presence of low molecular weight fraction of hydrolysable tannins such as nonahydroxytriphnoic, flavogallonic acid, ellagic and gallic acid, pentagalloylglucose and all sorts of degradation and oxidation products which are thought to be major components of valonea tannin. Moreover, castalagin/vescalagin and those added by a few residual structures/atoms, thus creating larger molecule and greater mass than castalagin/vescalagin, derived by internal rearrangements of a larger molecule constitute major components of valonea.