The pyrolysis behaviors of the three major organic components of eucalyptus alkaline peroxide mechanical pulping (APMP) spent liquor including alkali lignin (AL), lignin-carbohydrate complexes (LCC), and polysaccharide (PLS) were studied with emphasis on the effect and contributions of components on the overall pyrolysates of APMP spent liquor solid (ASLS). Profound differences on product properties from each component pyrolysis were illustrated. The results indicated that the bio-oil during ASLS pyrolysis was mainly attributed to AL, while the bio-gas and char were mostly affected by PLS. Small molecule hydrocarbons released during ASLS pyrolysis mainly came from AL and LCC, and CO and CO2 mainly produced from PLS. As for bio-oils, AL generated the largest proportion of monomeric phenols and aromatic hydrocarbons (AHs), while PLS and LCC mainly contributed to the production of ketones, furans and acids. The correlation shown here is of interest for further studies on pulping spent liquor grading utilization.