To determine the effect of volatile matter on combustion reactivity, the pyrolysis and combustion behavior of a set of four (R, C, M and K coals) coals and their chars has been investigated in a TGA (SDT Q600). The maximum reaction temperatures and maximum reaction rates of the coals and their chars with different heating rates (5-20 ℃/min) were analyzed and compared as well as their weight loss rates. The volatile matter had influence on decreasing the maximum reactivity temperature of low and medium rank coals (R, C and M coals), which have relatively high volatiles (9.5-43.0%), but for high rank coal (K coal) the maximum reactivity temperature was affected by reaction surface area rather than by its volatiles (3.9%). When the maximum reaction rates of a set of four coals were compared with those of their chars, the slopes of the maximum reaction rates for the medium rank coals (C and M coals) changed largely rather than those for the high and low rank coals (R and K coals) with increasing heating rates. This means that the fluidity of C and M coals was larger than that of their chars during combustion reaction. Consequently, for C and M coals, the activation energies are lower (24.5-28.1 kcal/mol) than their chars (29.3-35.9 kcal/mol), while the activation energies of R and K coals are higher (25.0-29.4 kcal/mol) than those of their chars (24.1-28.9 kcal/mol).