The ignition behavior of coal and biomass blends was assessed in air and oxy-firing conditions in an entrained flow reactor. Four coals of different rank, an anthracite, a semi-anthracite, and two high-volatile bituminous coals, were tested in air and O2/CO2 (21–35% O2) environments. For all the coals, deterioration in ignition properties was observed in the 21%O2/79%CO2 atmosphere in comparison with air. However, the ignition properties were enhanced when the oxygen concentration in the O2/CO2 mixture was increased. Coal and biomass blends of a semi-anthracite and a high-volatile bituminous coal with 10 and 20 wt% of olive residue were also used in the ignition experiments under air and oxy-firing conditions. The ignition behavior of the coals improved as the additions of biomass increased both in air and oxy-firing conditions. In particular, the effect of biomass blending was more noticeable in the ignition of the high rank coal. Since industrial oxy-coal combustion with a wet recycle would result in higher concentrations of H2O(v), the effect of steam addition on ignition behavior was also studied. A worsening in ignition behavior was observed when steam was added to the oxy-fuel combustion atmospheres, although an increase in the steam concentration from 10 to 20% did not produce any significant difference in the ignition characteristics of the fuels.