Although the phenomenon of hybrid entrepreneurs—individuals who work in paid and self-employment simultaneously—is prevalent, the psychological well-being of hybrid entrepreneurs has not been researched systematically to date. This is unlike research on paid employment and (assumed) full-time entrepreneurship, where psychological well-being has been researched as a key factor. Using data from the United Kingdom Household Longitudinal Survey, we address this void by studying whether hybrid entrepreneurs display distinct psychological well-being patterns (measured via mental strain, job satisfaction, and life satisfaction), utilizing a comparison with full-time paid employed, full-time self-employed and individuals working in two paid jobs. We further examine whether the specific work arrangements of hybrid entrepreneurs shape their well-being. To this end, we study the changes in well-being of hybrid entrepreneurs and other individuals in the comparison groups who switch to other jobs. For this purpose, we employed matching (entropy balancing approach) to account for self-selection effects. Our results suggest that the well-being of hybrid entrepreneurs is indeed distinct and can be explained by both self-selection effects and unique aspects of their work arrangements. Our study is thus the first to deliver evidence showing that hybrid entrepreneurs need to be studied as a separate group in entrepreneurship research concerned with well-being and psychological functioning. Our results have important implications not only for future research but also for practice.