Linalool is a monoterpene, which exhibits floral and spicy aromas as well as a variety of pharmacological effects, including antioxidant, anti-inflammatory, and cardiovascular. Wine flavor is highly dependent on the chemical compounds of berries. The objective of this study was to evaluate the concentration of volatile compounds, especially linalool, in grapes (Vitis vinifera L.) 'Muscat of Alexandria' grown under different cluster light exposure. Four defoliation treatments were applied at veraison, and changed the light environment at the fruit zone. Severe defoliation (T1): leaves were manually removed from the 1st to the 8th node of each shoot, partial defoliation (T2): leaves were manually removed from the 1st to the 4th, semi-shaded clusters (T3): un-trimmed vines were covered with an 80% shade netting; and (T4) control treatment with non-intervention during season 2014-2015. Free terpenes were extracted using headspace solid-phase microextraction (HS-SPME), and the concentration of volatile compounds was determined using gas chromatography coupled to a flame ionization detector (GC-FID). The study was conducted in two different locations of the Itata Valley in Chile. Linalool concentration was more prevalent in treatments with higher cluster exposure. The treatment with the highest defoliation showed a linalool concentration 40% higher than the control treatment. Higher levels of defoliation in grapevines grown under a traditional farming system result in an increased concentration of volatiles compounds, particularly monoterpenes, where Cerro Verde and Pinihue reached linalool concentrations of 19.1 and 21.7 mu g L-1, respectively. These results revealed important differences in the behavior of the synthesis of linalool.