Background: Steam explosion pretreatment has been examined in many studies for enhancing the enzymatic digestibility of lignocellulosic biomass and is currently the most common pretreatment method in commercial biorefineries. It is however not effective for overcoming the extremely high recalcitrance of softwood to biochemical conversion. Recent fundamental research in small-scale liquid hot water pretreatment has shown, though, that the addition of a carbocation scavenger like 2-naphthol can prevent lignin repolymerization and thus enhance the enzymatic digestibility of softwood cellulose. This work studies the technical application potential of this approach in a larger steam explosion pilot plant for surmounting softwood recalcitrance. Results: The addition of 35.36 g 2-naphthol to the steam explosion pretreatment of 1.5 kg spruce wood chips allowed to considerably enhance the enzymatic cellulose digestibility. Different ways of adding the solid 2-naphthol to steam pretreatment were tested. Mixing with the biomass before pretreatment could enhance digestibility by up to 55% compared to control experiments. Impregnation of the biomass with 2-naphthol was yet more effective. Acetone and ethanol were tested to dissolve 2-naphthol and impregnate the biomass. The solvents were then removed again by evaporation before the pretreatment. The impregnation allowed to enhance digestibility by up to 179 and 192%, respectively. A comparison to prevalent acid-catalyzed steam explosion pretreatments for softwood revealed that the scavenger approach allows for obtaining exceptionally high yields in enzymatic hydrolysis. The biomass impregnation with 2-naphthol even renders a complete enzymatic cellulose conversion possible, which is remarkable for a softwood pretreatment not removing lignin. Steam pretreatment experiments without explosive decompression revealed that the enhancing effects of the explosion and the scavenger complement each other well. The explosion enhances the accessibility of the cellulose while the use of the scavenger reduces particularly the deactivation of enzymes. Conclusions: This is the first study to show that a carbocation scavenger in steam pretreatment can enhance the enzymatic digestibility of lignocellulosic biomass. The approach opens up a novel possibility for overcoming the high softwood recalcitrance in a process that does not require an acid catalyst or the removal of lignin from the biomass.