Wine aroma is one of the most important parameters responsible for its quality, and hence for consumer acceptance. In order to obtain an appropriate technique to study volatile aroma compounds in mulberry wines, headspace-solid phase microextraction (HS-SPME) comb $40^{circ}C$ for 30 min with a $50/30{mu}m$ divinylbenzene-carboxen-polydimethylsiloxane (DVB-CAR-PDMS) fiber. Approximately 80 volatile compounds have been quantified in the mulberry wine, pertaining at several chemical groups, mainly higher alcohols, fatty acids, esters, and some volatile phenols whose concentration range from few to 138.36 mg/L. This work describes a novel methodology for the analysis of mulberry wines by HS-SPME coupled to GC-MS. HS-SPME using a $50/30{mu}m$ DVB-CAR-PDMS fiber is provided the higher extraction efficiency ($p$<0.05) for the volatiles including the most esters, higher alcohols, and fatty acids than by the other fibers.