This study aims to investigate the underlying dimensionality of the emotional self-efficacy scale (ESES) and determine its relationship with measures of ability emotional intelligence (EI) (Mayer–Salovey–Caruso EI Test), trait EI (Trait EI Questionnaire), personality, and cognitive ability. Participants included 822 undergraduate students and 263 graduates already in the workplace. Analyses of the data suggested a multidimensional factor structure for the ESES. The measure was found to correlate with trait EI and showed expected correlations with personality. It did not correlate with ability EI or cognitive ability. These findings are discussed and are interpreted as offering support for the use of the ESES as a reliable measure of emotional self-efficacy.