Entrepreneurs’ mental well-being has been a nascent research topic in the entrepreneurship domain, but it remains unclear whether and how entrepreneurship affects mental well-being in the context of emerging economies. Drawing on the self-determination theory (SDT), we developed a model in which entrepreneurship, compared to wage–employment, was identified as a career choice more conducive to work-related and socioeconomic status (SES)-related psychological functioning (i.e., work autonomy and subjective SES), which, in turn, produces mental well-being benefits. We tested this model in the Chinese context by providing evidence based on data from the Chinese General Social Survey (CGSS) between 2010 and 2021 (N = 28,419). We found that entrepreneurs had higher levels of positive mental well-being and lower levels of negative mental well-being than paid employees. Mediation analysis showed that subjective SES mediated the relationship between entrepreneurship and mental well-being and explained this relationship better than work autonomy. These findings indicated that the mental well-being benefits of entrepreneurship existed in emerging economies like China and highlighted the crucial role of SES-related psychological functioning in facilitating entrepreneurs’ mental well-being.