<p>This study develops and validates quantitative correlations linking cellulose crystallinity index (CrI) and degree of polymerization (DP) to hydrolysis efficiency across five lignocellulosic biomass feedstocks (pine needles, rice husk, wheat straw, sugarcane bagasse, and sunn hemp). Unlike previous studies that qualitatively linked these properties to hydrolysis performance, we establish power-law correlations that allow the glucose yield to be predicted directly from measurable structural characteristics of biomass. A microwave-assisted catalytic hydrolysis method was employed using a protic ionic liquid (PIL) and CuCl₂ catalyst, enabling rapid depolymerization under mild conditions. CrI ranged from 47.8% to 68.5% and DP from 735 to 1430, resulting in glucose yields between 28.6% and 50.8%. Pine needles (CrI 47.8%, DP 735) produced the highest glucose yield (50.8%), whereas sunn hemp (CrI 68.5%, DP 1430) showed the lowest yield (28.6%), confirming the inverse relationship between structural order and hydrolysis efficiency. Power-law relationships were established between glucose yield and CrI and DP, indicating their combined influence on hydrolysis performance. Molecular docking simulations supported these findings, demonstrating that PIL binds more favourably to shorter cellulose chains, with diminished interaction for longer, rigid structures that mimic crystalline domains. These results confirm that high CrI and DP jointly restrict solvent and catalyst accessibility to glycosidic linkages. This study provides mechanistic and quantitative evidence for the usefulness of CrI and DP as indicators of biomass quality, offering valuable direction for feedstock selection and optimization of pretreatment processes in the biofuel industry.</p> Graphical abstract <p></p>