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In this study we examined the relations conceptualized within Pekrun’s (2006) control-value theory (CVT). Specifically, we investigated the relations of control (science self-efficacy) and both positive and negative value with achievement emotions and achievement emotions with cognitive engagement, behavioral engagement, and science career intentions. Positive value positively related to positive activated emotions, negative value related positively to negative activated emotions, and science self-efficacy related positively to positive deactivated emotions and negatively to negative deactivated emotions. Positive and negative emotions were positively and negatively (respectively) associated with engagement and science career intentions. There were also significant interactions between positive value and control beliefs and indirect effects linking value and control beliefs with outcomes via emotions. Implications for CVT are discussed.