This paper presents an experimental and numerical study on co-firing olive waste (0, 10%, 20% on mass basis) with two coals in an entrained flow reactor under three oxyfuel conditions (21%O 2 /79%CO 2 , 30%O 2 /70%CO 2 and 35%O 2 /65%CO 2 ) and air-fuel condition. Co-firing biomass with coal was found to have favorable synergy effects in all the cases: it significantly improves the burnout while remarkably lowers NO x emissions. The reduced peak temperatures during co-firing can also help to mitigate deposition formation in real furnaces. Co-firing CO 2 -neutral biomass with coals under oxy-fuel conditions can achieve a below-zero CO 2 emission if the released CO 2 is captured and sequestered. The model-predicted burnout and gaseous emissions were compared against the experimental results. A very good agreement was observed, the differences in a range of ±5-10% of the experimental values, which indicates the model can be used to aid in design and optimization of large-scale biomass co-firing under oxy-fuel conditions.