Turkey annually produces 26 million tons of vegetables and is the third-biggest vegetable producer. After harvest, the waste of vegetable stalks lacking of economic value is burnt or left in the fields, causing environmental pollution. The aim of this study was to examine bioethanol production of a mixture of tomato, pepper, and eggplant stalks using an alternative chemical, sodium borohydrate (NaBH4) in a chemical pretreatment step. Both steam-exploded (SE) and dry-milled (DM) stalks were chemically pretreated and enzymatically hydrolyzed in this study. Results showed that SE stalks had better enzymatic digestibility compared to DM. NaOH treatment removed the highest amount of lignin (17.1%; SE, 2%, 90 min) but also glucose (21.5%; SE, 2%, 90 min) from the structure. On the other hand, NaBH4 removed the highest lignin in proportion to glucose for both SE and DM samples. Enzymatically hydrolyzed stalks gave the highest sugar yields of 30.1% (o.d.-dry matter) for the SE sample when it was pretreated with 2% NaOH for 30 min.