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Alkali metals inherent in black liquor (BL) have strong catalytic activity during gasification. A catalytic co-gasification process based on BL with pyrolysis oil (PO) has the potential to be a part of efficient and fuel-flexible biofuel production systems. The objective of the paper is to investigate how adding PO into BL alters fuel conversion under gasification conditions. First, the conversion times of single fuel droplet were observed in a flat flame burner under different conditions. Fuel conversion times of PO/BL mixtures were significantly lower than PO and comparable to BL. Initial droplet size (300–1500 μm) was the main variable affecting devolatilization, indicating control by external heat transfer. Char oxidation was affected by droplet size and the surrounding gas composition. Then, the intrinsic reactivity of char gasification was measured in an isothermal thermogravimetric analyser at T = 993–1133 K under the flow of CO 2 –N 2 mixtures. All the BL-based samples (100% BL, 20% PO/80% BL, and 30% PO/70% BL on mass basis) showed very high char conversion. Conversion rate of char gasification for PO/BL mixtures was comparable to that of pure BL although the fraction of alkali metal in char decreased because of mixing. The reactivities of BL and BL/PO chars were higher than the literature values for solid biomass and coal chars by several orders of magnitude. The combined results suggest that fuel mixtures containing up to 30% of PO on mass basis may be feasible in existing BL gasification technology. [ABSTRACT FROM AUTHOR]