The current study has focused on microwave-assisted pyrolysis of Dodonaea viscosa for producing bio-oil using two different catalyst types, HZSM-5 and TiO₂. The experiment included varying the microwave power (500–600 W), reaction time (5–20 minutes), and weight percentage of catalyst (20, 30, and 50 wt.%) to evaluate the effects of these variables on the product yield and proper bio-oil. The bio-oil were characterized through comprehensive methods, including GC–MS and physical/property measurements, including viscosity, pH, and higher heating values (HHV). The results show that the catalyst significantly affects both the quantity and quality of the bio-oil generated. TiO₂ showed the best results for bio-oil yield (32.42 wt. %) under 600 W and 20 minutes, indicating that it can facilitate controlled thermal decomposition while minimizing excessive secondary reactions. Conversely, HZSM-5 yielded a much lower maximum yield (25.7 wt%) at 500 W; however, it greatly improved the quality of the bio-oil. The HHV was increased to 25.4 MJ/kg when HZSM-5 was used instead of TiO₂ (21 MJ/kg). The GC–MS analysis demonstrated that HZSM-5 promoted deoxygenation/aromatization reactions, reactions leading to higher aromatic (21.3%) and phenol (21.57%) and lower oxygenated compounds such as acids (12.9%). On the contrary, TiO₂ had a larger proportion of ketone (%18.2) and acid (%17.1); these data reflect a moderate catalytic activity for TiO₂ and less potential for upgrading bio-oil. In general, this study indicates that TiO₂ is more efficient at increasing bio-oil yields, whereas HZSM-5 is better at enhancing bio-oil quality.