Research indicates the value of examining how specific Positive Emotionality (PE) facets relate to psychopathology, but the facet-level structure of PE remains unclear. Previous factor analyses of PE-related scales provided evidence for a four-factor structure of Elation, Attentiveness, Excitement Seeking, and Warmth. With the exception of Attentiveness, which emerged as a more general facet and was labeled Cheerfulness, this structure replicated in the current sample. These four factors then were related to psychopathology measures assessing internalizing, externalizing, and psychotic symptoms. Excitement Seeking showed considerable specificity, as it associated more strongly with externalizing than internalizing symptoms, demonstrating especially strong relations with risk taking, attention seeking, manipulativeness, and impulsivity. Cheerfulness and Elation related negatively to internalizing symptoms, and the former also showed moderate negative relations with externalizing symptoms such as distractibility and drug use. Warmth had mostly weak relations, although it showed notable negative correlations with antisocial symptoms.