Two established delignification methods employing sodium chlorite-acetic acid (SC/AA) and peracetic acid (PAA) are often used, and are reportedly highly selective. However, these reports are mostly for highly recalcitrant and unpretreated softwoods and hardwoods species, and information for less recalcitrant lignocellulosic feedstocks and pretreated biomass is scarce. Furthermore, the effects on cellulose structure are not documented. Thus, in this study, delignification kinetics and selectivity were evaluated when SC/AA and PM were applied to untreated switchgrass, poplar, corn stover, and pine sawdust; poplar subjected to AFEX, controlled pH, lime, and SO2 pretreatments; and the cellulose model compounds. Both methods proved effective in removing >90% lignin, but selectivity for lignin and carbohydrates removal was substrate and pretreatment dependent. For untreated biomass, PAA was more selective in removing lignin than SC/AA; however, both methods were less selective for pretreated solids. Cellulose characterizations revealed that PAA had less pronounced impacts on cellulose structure. (C) 2012 Elsevier Ltd. All rights reserved.