This study was aimed to analyze the effect of temperature (40, 60, and 80 ºC) and time (10, 40, and 80 min) on extraction of major volatile compounds (VC) from piquin peppers (Capsicum annuum L. var. glabriusculum) using HS-SPME. VC extraction was significantly affected (P<0.05) by temperature and time, which was described by a kinetic fractional conversion equation and the Arrhenius model. However, principal component analysis (PCA) performed on major VC determined a differential response of VC to extraction conditions. Two distinctive groups of compounds were identified using kinetic and statistical criteria: compounds associated (GR1) and poorly associated (GR2) with the aromatic profile of peppers. Extraction of GR1 compounds was favored at 40 oC and 80 min; whereas for GR2, extraction was favored at 80 oC and 80 min. The best extraction condition of VC associated with aroma of piquin pepper was determined (40 ºC and 80 min) considering the individual effect of temperature that favored extraction of VC within GR1. The results showed that the use PCA can be a useful tool for a better selection of extraction conditions of the aromatic fraction of interest.