Beyond the conventional consideration of pretreatment severity (PS) responsible for biomass disruption, the influence of reagent properties on biomass (LCB) disruption is often overlooked. To investigate the LCB disruption as a function of reagent properties, reagents with distinct cations (NaOH and KOH) and significantly higher delignification potential were chosen. NaOH solution (3 % w/v) with a measured pH of 13.05 ± 0.01 is considered the reference, against which a KOH solution (pH = 13.05 ± 0.01) was prepared for LCB pretreatment under the same PS. Despite comparable lignin content, varying glucose yield of NaOH (68.76 %) and KOH (46.88 %) pretreated residues indicated the presence of heterogeneously disrupted substrate. Holocellulose extracted from raw poplar (ASC, control) and alkaline pretreated residues (C-NaOH and C-KOH) were analyzed using HPLC, XRD, SEM, TGA/DTG, XPS, and 13CP MAS NMR to investigate the pretreatment-induced structural modification. Results revealed that, despite the same pretreatment severity, better disruption in C-NaOH (higher accessible fibril surface and less-ordered region) leading to higher digestibility than C-KOH, likely due to the smaller ionic radius of Na+, facilitates better penetration into dense LCB matrix. This study elucidates the importance of considering the reagent properties during LCB pretreatment, eventually enhancing consciousness while selecting reagents for efficient LCB utilization.