Most future educational and career transitions represent major life events that individuals anticipate to a considerable extent, possibly with multiple emotions at the same time. However, few studies have examined the emotions that individuals experience when they anticipate a future educational or career transition, imagine how it will occur, the consequences it will have for them, and visualize their coping efforts. The aims of the present dissertation are fourfold. First, we explore individuals’ combinations of multiple future-oriented emotions at the prospect of three major educational and career transitions: (a) the transition from high school to higher education, (b) the transition from higher education to the job market, and (c) the transition from unemployment to employment. Due to the rather exploratory nature of our first research question, our second objective pertains to the replication of these combinations and the investigation of similarities between several groups of individuals based on (a) gender, (b) institutional context, and (c) the temporal distance before the transition. Third, we examine several antecedents of individuals’ combinations of future-oriented emotions. These antecedents ranged from career-related constructs such as career decidedness and career adaptability to affective mechanisms such as cognitive appraisals, trait affect, and emotion regulation. Finally, we examine the behavioral effects of future-oriented emotions in terms of anticipated vocational planning and effort. Overall, the present dissertation brings several implications in highlighting the combinations of future-oriented emotions that individuals experience when anticipating important vocational transitions, a research strand that is scarce both in vocational and emotion research. From a practical point of view, the evidence of several combinations—and the differences and similarities among several groups or contexts—carries practical implications for designing and implementing career-related interventions. Finally, examining antecedents and outcomes of future-oriented emotions combinations underlines the importance of taking emotional anticipation processes into account when individuals prepare for and cope with major educational and career transitions.