The new approach used to find extractives, holocellulose and total lignin from typical Brazilian biomass residues was optimized through the Response Surface Methodology (RSM) in the present study. The effects of different reaction conditions, including the hydrolysis reaction and extraction time, as well as the alcohol substrate molar ratio were investigated. A quadratic polynomial regression model was used to analyze the experimental data. The coefficient of determination was higher than 0.85 and the model was considered to be adequate. The obtained data showed that the methodologies by the National Renewable Energy Laboratory must meet each biomass type. These data can be now applied to large-scale biomass fuel production using the optimized results.