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There is little doubt that currently trait EI (Trait emotional intelligence) theory and their measures have been found valid and reliable in several research and application settings. This research provides psychometric evidence of the TEIQue-SF in Chilean general and clinical population sample ( n 1  = 335, n 2  = 120). The results confirmed the factor structure of the instrument and supported its multidimensionality. Hierarchical and bi-factor CFA models with the Spanish-Chilean-TEIQue-SF analyzed its internal structure in the R environment, following the assessment of bi-factor ESEM models in Mplus. We performed these analyses both at the global and factor- level. CFA models did not reach acceptable fit statistics for the models, whereas ESEM models reached good to excellent fit for the bi-factor models proposed. We also implemented measurement invariance analyses, which provided evidence for full measurement invariance between the original UK validation sample and the Chilean samples up to the scalar level. Also, the means for the global trait EI factor and the four factors (Well-being, Self-control, Emotionality and Sociability) were alike previous psychometric research with the questionnaire. The results highlight the importance of performing multidimensional factor analysis through ESEM following a bi-factor interpretation of the TEIQue-SF internal structure.