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. This work was carried out with financial support from the Spanish MICINN (Project PS-120000-2005-2) co-financed by the European Regional Development Fund. L.A. and M.V.G. acknowledge funding from the CSIC JAE programs, co-financed by the European Social Fund. J.R. acknowledges funding from the Government of the Principado de Asturias (Severo Ochoa program), respectively. Support from the CSIC (PIE 201080E09) is gratefully acknowledged. Peer reviewed