<p>The use of biomass as an energy source, replacing fossil fuels, is more sustainable. Biomass is renewable, low-cost, and, when produced properly, can have a net carbon cycle. This factor has driven research in several areas, such as the production of biofuels and pyrolysis processes to produce bio-oil. Pyrolysis is a promising technique for converting lignocellulosic biomass into liquid, solid, and gaseous products. Catalytic pyrolysis is a promising method that improves the quality of bio-oil produced from biomass. This study investigates the pyrolysis of three types of lignocellulosic biomass: <i>Coffea canephora</i> (coffee straw) and clonal residues (canopy and bark) of <i>Eucalyptus grandis</i> x <i>Eucalyptus urophylla</i>. These biomass types are abundant, renewable, and contribute to waste valorization, aligning with sustainability goals by converting agricultural and forestry residues into bio-oil, a potential alternative to petroleum products. Pyrolysis experiments were conducted at four temperatures (300, 400, 500, and 600 °C) and involved two catalysts, copper oxide (CuO) and titanium dioxide (TiO₂), to enhance bio-oil quality. With the aid of a pyrolyzer coupled to gas chromatography/mass spectrometry (Py-GC/MS), the yields and quality of the products were obtained. The biomasses were characterized according to their chemical and physical composition. Results indicate that coffee straw produced the highest acetic acid yields without a catalyst, while CuO significantly boosted furfural yield. For levoglucosan, canopy residues treated with CuO yielded the best results. However, bark residues showed limited potential for high-value product yields. These findings highlight the potential of coffee straw and canopy residues for producing valuable chemical compounds through catalytic pyrolysis, presenting a pathway for sustainable biomass utilization.</p> Graphical Abstract <p></p>