This study draws on labeling theory and education research on the steps to college enrollment to examine 1) whether and for how long arrest reduces the likelihood that high‐school graduates will enroll in postsecondary education and 2) whether any observed relationships are mediated by key steps in the college enrollment process. With 17 years of data from the National Longitudinal Survey of Youth 1997 (NLSY97) and propensity score matching, we derived matched samples of arrested and nonarrested but equivalent youth (N = 1,761) and conducted logistic regression and survival analyses among the matched samples to examine the short‐ and long‐term postsecondary consequences of arrest. The results revealed that arrest reduced the odds of 4‐year college enrollment directly after high school, as well as that high‐school grade point average and advanced coursework accounted for 58 percent of this relationship. The results also revealed that arrest had an enduring impact on 4‐year college attendance that extended into and beyond emerging adulthood. Two‐year college prospects were largely unaffected by arrest. These findings imply that being arrested during high school represents a negative turning point in youths’ educational trajectory that is, in part, a result of having a less competitive college application. Implications are discussed.