Two fractions of sugarcane, namely bagasse and straw (or trash), were characterized in relation to their chemical composition. Bagasse presented values of glucans, hemicelluloses, lignin and ash of 37.74, 27.23, 20.57 and 6.53%, respectively, while straw had 33.77, 27.38, 21.28 and 6.23% of these same components. Ash content was relatively high in both cane biomass fractions. Bagasse showed higher levels of contaminating oxides while straw had a higher content of alkaline and alkaline-earth oxides. A comparison between the polysaccharide chemical compositions of these lignocellulosic materials suggests that similar amounts of fermentable sugars are expected to arise from their optimal pretreatment and enzymatic hydrolysis. Details about the chemical properties of cane biomass holocellulose, hemicelluloses A and B and α-cellulose are provided, and these may offer a good opportunity for designing more efficient enzyme cocktails for substrate saccharification.