The studies carried out on biomass pyrolysis indicate that cellulose, hemicellulose, and lignin are solely responsible for the chemical composition of bio-oil. However, few studies refer to extractives as a relatively significant biomass fraction in bio-oil composition. This work aims to study the influence of hydrophilic extractives on the quality of bio-oil using sugar cane bagasse, sisal, and eucalyptus bark residue. The extractives were separated from the biomasses, using ethanol and water as solvents due to their polarity and efficiency in extracting hydrophilic compounds. Three materials were obtained: biomass before and after extraction and extractives. GC-MS was used to identify the species that compose the extractives and the micro-pyrolysis products at 550°C of the three materials. As expected, the results showed that the bio-oils had different compositions. While bio-oils derived from sugarcane bagasse and eucalyptus bark residue exhibited higher levels of aldehydes (23%), bio-oil from sisal residue contained approximately 47% hydrocarbons. Finally, extractives also influenced CO2 production, as evidenced by notable variations in the range of 52.6–75.3% of this compound during the pyrolysis of biomass extractives. These differences are especially notable in biomasses with higher extractive contents, such as sisal (69.3%) and eucalyptus bark (21.9%) residues.