The present invention discloses polyelectrolyte complexes (PECs), e.g. water insoluble PECs, obtained by reacting a negatively charged hemicellulose-lignin co-polymer with a cationic polymer. The negatively charged hemicellulose-lignin co-polymers is selected from lignin carbohydrate complexes (LCC) from pre-hydrolysis sulphite pulping, LCC from pre-hydrolysis kraft pulping, LCC from mechanical pulping and chemical/mechanical pulping (TMP and CTMP). The cationic polymer is selected from cationic polysaccharides and cationic starches. Methods for production of PECs, are also disclosed.