Pyrolysis conditions and the presence of ash-forming elements significantly influence char properties and its oxidation or gasification reactivity. In this study, intrinsic gasification rates of char from high heating rate pyrolysis were analyzed with isothermal thermogravimetry. The char particles were prepared from two biomasses at three size ranges and at two temperatures. Reactivity dependence on original particle size was found only for small wood particles that had higher intrinsic char gasification rates. Pyrolysis temperature had no significant effect on char reactivity within the range tested. Observations of ash formation highlighted that reactivity was influenced by the presence of ash-forming elements, not only at the active char sites but also through prohibition of contact between char and gasification agent by ash layer formation with properties highly depending on ash composition.