Understanding the gap between students’ aspirations for postsecondary education and their actual postsecondary attainment is key to understanding and reducing educational and vocational inequities. Just as work volition has emerged as a key factor in understanding access to decent work, students’ sense of control over or volition in the college-going process may be a key factor in understanding their access to postsecondary education. In the current study, we adapted a common measure of work volition to create a measure of college-going volition (CGV). In a large sample of rural Appalachian high school students, the measure showed good psychometric properties and strong measurement invariance across gender and prospective college-generation groups. There were no gender differences in CGV, but prospective first-generation college students demonstrated significantly lower CGV than their continuing-generation peers. CGV also accounted for significant unique variance in college-going self-efficacy beyond educational barriers.