Lignocellulosic biomass represents an excellent alternative to fossil fuels in terms of both energy production and raw material usage for a plethora of daily-use products. Organosolv pretreatment is a fractionation technique able to separate lignocellulosic biomass into individual streams of cellulose, hemicellulose, and lignin under controlled conditions. Sawdust, the by-product of sawmill processing of Picea abies wood, was the subject of our investigation in this work. The aim was to evaluate the effects of different parameters of the organosolv process of spruce sawdust on the yield of components and how this affects the enzymatic saccharification of cellulose. Sixteen distinct pretreatments were performed with ethanol concentrations of 50 and 60% v/v at 180 and 200 °C for 15 and 30 min. Half of the pretreatments contained 1% sulfuric acid as a catalyst, while the other half were acid-free. Thereafter, the effects of different variables on the yield of products were assessed and compared to determine the ideal pretreatment condition. The results showed that cellulose-rich pulps, with cellulose content as high as 55% were generated from an initial mass of 37.7% spruce sawdust with the reactor operating at 180 °C for 30 min using 60% ethanol and 1% sulfuric acid. With the pretreatments performed with the catalyst at 200 °C, hemicellulose was almost entirely removed from the pulps obtained. The recovered hemicellulose fraction was composed mainly of monomers achieving up to 10 g/100 g of biomass. Delignification values of up to 65.7% were achieved with this pretreatment technique. Fractionated lignin presented low levels of sugar and ashes contamination, with values as low as 1.29% w/w. Enzymatic saccharification of the pretreated pulps yielded 78% cellulose hydrolysis, with glucose release higher than 0.54 g/g of biomass, indicating the potential of the pulps to be applied in a fermentation process.