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• Char activity in volatile-char interactions varies with biomass components. • Xylan char rich in C O group is the most active for (benzyloxy)benzene conversion. • Char C(sp2) O group promotes the breaking of C(sp3) O in (benzyloxy)benzene. • Char C(sp3) O group promotes the breaking of C(sp2) O in (benzyloxy)benzene. • Lignin char is highly selective to monomers due to the abundant C O group. Char activity is a critical factor for the interactions between char and volatile, which are recognized to determine the final product distribution from biomass pyrolysis. To clarify the effect of biomass composition on char activity, the interactions between (benzyloxy)benzene as a volatile model compound and char samples obtained from cellulose, xylan, and lignin were studied. The (benzyloxy)benzene conversion increased from 0.64 % for no char to 6.31 %, 6.98 % and 53.5 % for lignin char, cellulose char, and xylan char, respectively, which were mainly derived from the contribution of surface C O groups and surface defects in the carbon structure. Especially, surface C(sp2) O groups and C(sp3) O groups on char respectively favored the breakage of C(sp3) O and C(sp2) O bonds in (benzyloxy)benzene. Despite the low activity, lignin char showed high selectivity to monomeric products due to the high content of surface C O groups, which were considered to induce the production of hydrogen radicals to stabilize the resulting intermediates. The findings of this study prove that the volatile-char interaction could be adjusted facilely by changing the hemicellulose content during feedstock pretreatments. [ABSTRACT FROM AUTHOR]