This study investigates the relationship between postsecondary aspirations and vocational/educational self-efficacy beliefs, outcome expectations, perceived educational barriers, and sources of support among a sample of rural Appalachian high school students. Using Social Cognitive Career Theory as the theoretical framework, vocational/educational aspirations are examined in terms of four specific postsecondary pathways common to rural Appalachian students (work, vocational technical, bachelor's only, and professional). Results indicated vocational/educational self-efficacy beliefs, college outcome expectations, likelihood of encountering barriers to postsecondary education, and socioeconomic status contribute significantly to the discriminant function predicting the post-secondary pathways. This research extends previous work in this area by examining an understudied group, rural Appalachian adolescents. Implications of the results and suggestions for future research are provided. (Contains 3 tables.)