Many bioproducts are generated by applying enzymes to lignocellulosic biomass that deconstruct polysaccharides into fermentable sugars. However, the components of lignocellulosic biomass (and their integration) have molecular-scale structure and nano-/meso-scale architectures designed by nature to resist biological or environmental sources of degradation. This resistance to deconstruction (biomass recalcitrance) makes biomass difficult and expensive to use as a feedstock for bioproduct generation. For example, pretreatments must be applied prior to polysaccharide enzymatic hydrolysis to obtain viable conversion performance. We have projects focused on studying and understanding the fundamental issues relevant to biomass recalcitrance therefore requires the application and integration of multiple analytical techniques that probe biomass molecular/architectural features.