In this chapter the authors argue that personal values influence motivation and intention to exploit business ideas. The aim is to investigate which values direct individuals willing to start up their ventures out of an opportunity, compared to those who would start their venture out of necessity. To address this aim, the authors combine the literature on entrepreneurial intentions and opportunity-driven entrepreneurship with psychological knowledge on individual values. By applying Schwartz’s theory of personal values on a sample of 2974 adults from Spain, the authors examine how values organized along two bipolar dimensions – openness versus conservation and self-enhancement versus self-transcendence – influence the perceived likelihood of an individual entering entrepreneurship ‘to take advantage of an opportunity’ or ‘out of necessity’. The study indicates that openness to change and self-enhancement encourage opportunity-driven entrepreneurship, while conservation and self-transcendence stimulate necessity-based entrepreneurship. The study also confirms that the start-up intention is mostly connected with exploiting a potential opportunity. Entrepreneurial intention mediates the relationship from the motivational antecedents to the opportunity motives. The study’s contribution is a new, value-based insight into the sources of two classes of entrepreneurship. By identifying the value priorities held by individuals who exploit opportunities, the chapter advances the understanding of value-laden entrepreneurial intentions leading to entrepreneurial behaviours.