Bark wastes today are viewed as a high-value resource for biorefinery due to their chemical richness and diversity. This work presents a comprehensive chemical characterization of the inner bark and the outer bark of Eucalyptus camaldulensis cultivated in Algeria. The extractives were first isolated with an Accelerated Solvent Extractor (ASE) and then analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). The content of pre-extracted bark in cellulosic polysaccharide and free sugar monomers was determined by Gas Chromatography (GC). The hemicellulose composition and amount was determined after the acid methanolysis and GC. The amount of lignin was determined gravimetrically by the Klason lignin method and the acid soluble lignin was determined by the UV method. Formic and acetic acids in the bark were determined by HPLC after alkaline hydrolysis. It was found that the extractives content were similar in the outer bark (0.85%) and the inner bark (0.88%). The cellulose content was higher in the outer bark (33.4%) than in the inner bark (28.7%). Lignin and the total hemicellulose contents were more abundant in the outer bark (31.7, 26.2%) than in the inner bark (28.6, 19.3%) whereas, sugar monomers were more abundant in the inner bark (4.4%) than in the outer bark (3.8%). The variation in acetic and formic acids and ash contents between the outer bark (1.5, 0.006 and 2.5%) and the inner bark (1.3, 0.005 and 2.4%) was small. The obtained results showed that the bark can be considered a suitable feedstock for lignocellulosic biorefinery and also for the extraction of bioactive compounds that can be used in different sectors.