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Several definitions and measures of financial well-being (FWB) have been proposed in the scientific literature. The Multidimensional Subjective Financial Well-being Scale (MSFWBS) stands out among these measures in its ability to account for the conceptual richness of FWB. However, the original validation study based on a confirmatory factor analytic model indicated that the factor structure of scores obtained on this instrument was acceptable at best, revealing factor correlations high enough to question the discriminant validity of the factors. To improve conceptual and operational clarity of FWB, this study assesses the psychometric properties of the MSFWBS among French-Canadian adults (n = 454), using statistical models better suited to the examination of multidimensional constructs (exploratory structural equation modeling-ESEM, and bifactor-ESEM). Our results supported a bifactor-ESEM representation of scores on the MSFWBS, and their measurement invariance across groups of participants defined on the basis of their age, sex, personal income and household income. Our results also supported the convergent (with other measures of FWB) and criterion-related (with measures of life satisfaction, perceived stress, and psychological distress) validity of scores obtained on the MSFWBS (particularly the global FWB factor). By providing an optimized measure of FWB, our study contributes to advancing research on FWB.