In this study, selective extraction towards ionic liquid trihexyltetradecylphosphonium chloride ([P66614]Cl) of lignin residues, polysaccharides and organic acids present in black liquor (BL), the main principal wastewater of pulping industry was studied. With the objective of finding optimized conditions allowing to extract lignin residues while polysaccharides and organic acids remain in aqueous solution, a design of experiments approach based on a response surface methodology was used. Three continuous factors, namely initial pH varying from 9 to 13.5, dilution of BL varying from 5 to 20 and volumetric ratio of black liquor vs. ionic liquid RV., varying from 1 to 19, were investigated. Concentration of lignin residues, polysaccharides and organic acids were measured using Folin-Ciocalteu method, the anthrone method and HPLC, respectively. Results showed that a multi-response optimization led to the extraction of 84.8 % of lignin residues, 66.0 % of polysaccharides, and no extraction of OA under optimised conditions.