The FIRST (Feedstock Impregnation and Rapid Steam Treatment) approach was used in this study to isolate extractives, hemicellulose, lignin, fibers, and cellulosic fines of softwood. With hydrolysis and fermentation of the hemicellulose and cellulosic fines fractions, this approach produces four co-products: extractives, cellulose, lignin, and ethanol. The first unit operation uses aqueous/ alcohol to remove and recover the extractive rich fraction. The second unit operation uses steam treatment to destructure the matrix and solubilize a large fraction of the hemicelluloses. The third unit operation uses alkaline delignification to dissolve a lignin fraction. The fourth unit operation uses the refining process to separate fibers from cellulosic fines. The fibers are bleached. The yields of lignin and bleached cellulose were about 20.0 kg and 38.3 kg out of 100 kg initial dry pine, respectively. The recovered hemicelluloses were 23.3 kg (containing 16.1 kg hexoses and 5.0 kg pentoses) and the cellulose fines derived hexoses amounted to 3.4 kg out of 100 kg initial dry pine. When the two liquors containing the hemicellulose sugars and the cellulose fines-derived hexoses were fermented for ethanol production, an ethanol yield of 6.8 kg was obtained.