Sugarcane straw, consisting of green tops and dry leaves, can be maintained on fields to improve soil quality, or harvested for bioenergy production. The optimum option between these two uses is still uncertain and requires further study. This study, conducted across three crop cycles, provides an assessment of the moisture, nutrients, ash, extractives, cellulose, hemicelluloses, and lignin contents of four sugarcane varieties across seven regions of south‐central Brazil. Suitability of the straw fractions for nutrient recycling, bioelectricity, and second‐generation ethanol production were also evaluated. Results showed that the sugarcane straw yield (dry mass) was 14.0 Mg ha−1, and the ratio of dry straw/fresh stalk was 12%. The composition of green tops and dry leaves differed consistently across varieties, sites, and crop cycles. Dry leaves represented 60% of the straw, but green tops contained about 70% of the total N, P, and K content. Therefore, green tops recycled up to four times more nutrients than dry leaves. Green tops also had six times higher moisture and greater chlorine content which decreased the mill process efficiency. In turn, dry leaves had higher lignin, cellulose, and hemicelluloses content, greater heating value (higher: 17.3 MJ kg−1; lower: 15.6 MJ kg−1) and tended to be a better second‐generation ethanol production feedstock. Overall, the results show that it is preferable to use dry leaves for bioenergy production while leaving green tops on the field for nutrient recycling. This study pointed out that more efficient methods for separating these fractions in the field need to be developed. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd