In this work, liquid hot water pretreatment (autohydrolysis) was used to improve enzymatic hydrolysis of a commonly consumed vegetable waste in Spain, Italian green pepper, to finally produce fermentable sugars. Firstly, the effect of temperature and contact time on sugar recovery during pretreatment (in insoluble solid and liquid fraction) was studied in detail. Then, enzymatic hydrolysis using commercial cellulase was performed with the insoluble solid resulting from pretreatment. The objective was to compare results with and without pretreatment. The results showed that the pretreatment step was effective to facilitate the sugars release in enzymatic hydrolysis, increasing the global sugar yield. This was especially notable when pretreatment was carried out at 180 °C for 40 min for glucose yields. In these conditions a global glucose yield of 61.02% was obtained. In addition, very low concentrations of phenolic compounds (ranging from 69.12 to 82.24 mg/L) were found in the liquid fraction from enzymatic hydrolysis, decreasing the possibility of fermentation inhibition produced by these components. Results showed that Italian green pepper is an interesting feedstock to obtain free sugars and prevent the enormous quantity of this food waste discarded annually.