Entrepreneurs are critical for countries’ industrial dynamics and economic growth. Although there are several studies focusing on the attitudes, cognitions and traits of entrepreneurs, only a few have explored the link between entrepreneurship and the job features entrepreneurs most value in the work setting. Taking a longitudinal perspective, over two periods of time, 1990–1993 and 2008–2010, the present study resorted to the European Value Study dataset, encompassing 27 European countries and more than 100 thousand individuals. Based on logistic estimates, we found that, compared with non-entrepreneurs, entrepreneurs consider work more important than other life dimensions (except family). Moreover, some work values associated with entrepreneurship (e.g., use initiative, achieving something, responsible job, meeting abilities, have a say, and learning new skills) are indeed mentioned the most by entrepreneurs and emerged significantly related with entrepreneurial propensity. Finally, some work values (e.g., have a say) are associated with entrepreneurship propensity regardless of country’s culture, whereas others (e.g., interesting job) are strongly influenced by culture.