During the last decade, many efforts have been made in pulp and paper industry to construct more effective, sustainable and environmentally friendly pulp bleaching sequences. In this work, enzymatic (laccase-mediator system, L), non-oxidative chemical (urea, U) and mechanical (PFI refining, R) treatments have been conducted, alone or in a combination, on unbleached eucalyptus kraft pulps to evaluate their bleaching effects and thus the further potential as additional treatment(s) on a conventional bleaching process. The pulps obtained were characterized in terms of kappa number, hexenuronic acid content, brightness and viscosity. Moreover, the lignin-carbohydrates complexes (LCCs) were fractionated and characterized concerning lignin content and carbohydrate composition and for (HNMR)-H-1 and thioacidolysis-GC and-SEC analysis. It has been found that the effect of the L treatment was limited at delignification by a kappa number reduction of 0.8 units. The effects of the U treatment included delignification (1.4 kappa units), HexA removal (3 mol/g) and pulp brightening (3.4 ISO units). The refining darkened the pulp (3 ISO units) while the subsequent L or U treatment could bleached more than without the R stage. The delignification extent by all the treatments could be noticed also from the isolation yields of the LCC1 (glucan-lignin) fraction. Thioacidolysis-SEC analysis revealed the darkening mechanism of the R treatment and the delignification mechanisms of L and U treatment, showing that the L treatment removed more effectively the condensed parts of the lignin located at LCC2 (xylan-lignin) fraction.