The recognition and exploitation of opportunities is at the heart of entrepreneurship. As a consequence, in the last decades, the importance of alertness construct has increased. To date, however, entrepreneurial alertness has been mostly viewed and studied within the field of entrepreneurship but recently it increasingly became relevant also for the career construct of the people. Accordingly, scholars have argued for the crucial role of alertness to opportunities in the modern career research and practice. Consequently, integrating entrepreneurial alertness into the career development literature would inform inquiry into understanding and developing contemporary career development outcomes, such as employability. Moreover, the entrepreneurial alertness construct has been studied identifying three different components: alert scanning and search, alert association and opportunity evaluation but the understanding and a test of the interaction of these three entrepreneurial alertness dimensions is missing. Starting from these theoretical premises and based on a web-survey and a structural equation model (SEM) analysis, which involved 406 students of the University of Florence, this study wants to contribute in two different ways. First, this research tested the causality steps of entrepreneurial alertness and demonstrated that this cognitive construct is a sequential process which involves: alert scanning and search, alert association and opportunity evaluation. Secondly, this study wants to contribute at the new emergent field of study which considers entrepreneurial alertness as an important cognitive process for career development. Specifically, thanks to our contribution we demonstrated that entrepreneurial alertness, as a cognitive process, is determinant for the self-perceived employability.