The purpose of the current online cross-sectional study was to examine the relationship between hope, core self-evaluations (CSE), emotional well-being, health-risk behaviors, and academic performance in students enrolled in their first year of college. Freshmen (N = 495) attending a large public university in the Northeastern United States completed an online survey between February 1 and 13, 2017. Linear regression, path analysis, and structural equation modeling procedures were performed. CSE mediated the relationship between hope and emotional well-being and academic performance. Contrary to the hypotheses, higher hope predicted more sexual risk-taking behaviors and alcohol use. CSE is an important component of Hope Theory, which is useful for predicting emotional well-being and academic performance, but not as useful for predicting drug use, alcohol use, and sexual risk taking. Hope and CSE interventions are needed to improve academic performance and emotional well-being in university freshmen.