Positive (PA) and negative affect (NA) are related with aspects that are part of people’s psychological well-being, and the possibility of combining both dimensions to create four affective profiles, self-fulfilling (high PA and low NA), low affective (low PA and low NA), high affective (high PA and high NA) and self-destructive (low PA and high NA), has recently appeared. The current work aims to validate the short version of the Positive and Negative Affect Schedule (PANAS) in Ecuador, test the existence of the four affective profiles and analyze its relation with social anxiety. The Positive and Negative Affect Schedule for Children and the Social Anxiety Scale for Adolescents was employed in a sample of 1786 Ecuadorian students aged from 15 to 18 years (M = 16.31, SD = 1.01). The factorial invariance of the scale across sex and age groups was proved and latent mean analyses showed that girls and 18-year-old students obtained the highest scores in negative affect. With regard to the affective profiles, the cluster analyses confirmed the existence of the four mentioned profiles, and the self-fulfilling profile obtained the lowest scores in all the dimensions of social anxiety, whereas the self-destructive profile obtained the highest scores.