In order to promote convenient strategies for the valorization of Aucoumea klaineana Pierre (Okoume) plywood and sawmill wastes industry in the fields of adhesives and composites, the total phenolic content of Okoume bark, sapwood and heartwood was measured. The molecular structure of tannins extracted from the bark was determined by Matrix Assisted Laser Desorption/Ionization Time-Of-Flight (Maldi-ToF) mass spectrometry and Fourier transform infrared spectroscopy (FTIR). The total phenolic content displayed significant difference (p = 0.001) between the bark, sapwood and heartwood which decreased as follows: 6 ± 0.4, 2 ± 0.8 and 0.7 ± 0.1% respectively. The pro-anthocyanidins content was also significantly different (p = 0.01) among the three wood wastes, and the bark was the richest in condensed tannins (4.2 ± 0.4%) compared to the sapwood (0.5 ± 0.1%) and heartwood (0.2 ± 0.2%). Liquid chromatography coupled mass spectroscopy (LC-MS) and Maldi-ToF analysis of the bark showed for the first time that Okoume condensed tannins are fisetinidin, gallocatechin and trihydroxyflavan based monomers and complex polymers obtained with glycosylated units. No free catechin or robitinidin units were detected, whereas distinctive dihydroxy or trihydroxyflavan-3-benzoate dimers were observed in the investigated condensed tannin extracts. FTIR analysis showed the occurrence of glucan- and mannan-like sugars in the condensed tannins, and Maldi-ToF highlighted that these sugars should account for ten glycosylated units chemically bonded with two fisetinidins and one gallocatechin trimer. The condensation of these polyphenols with formaldehyde led to Stiasny numbers of 83.3, 73.3 and 53.3% for the bark, sapwood and heartwood, respectively.