Catalytic fast pyrolysis of cassava stalks has been intriguing as a promising, feasible chemical refinery method in terms of waste-to-energy conversion from cassava cultivation. This study aims to determine the synergetic influence of Mo and Co on Ni catalysts (Ni, Ni–Mo, and Ni–Co) prepared via ultrasonic-assisted incipient wetness impregnation method for catalytic pyrolysis vapor upgrading. The results indicated that Co and Mo enhance the reducibility of NiO and promote weak-to-medium acidity, thereby enhancing Ni's performance. Mono-Ni favors cracking deoxygenation, whereas oxophilicity promoters particularly enhance the oxygen absorbability efficiency to selective deoxygenated production. A fine Ni dispersion on CoNi/SiO2 catalyst was observed to positively affect the production of monoaromatic hydrocarbons (46.10 %), in contrast to those without promoters (21.63 %). This is attributed to an optimal Ni-metallic distribution with a small crystal size of 7.01 nm and a high surface area of 342.6 m2 g−1, highlighting the effectiveness of the promoter-assisted Ni catalyst. Additionally, a high yield of H2 (66.9 %) in non-condensable gas was recorded at 550 °C. The study suggests that a simplified approach to developing Ni-based catalysts could enhance the eco-friendliness of commercial catalysts, thereby facilitating the scale-up of biomass pyrolysis applications.