Purpose The School-to-Work (STW) Opportunities Act was passed to aid students in transitioning from education to employment by offering work-based learning opportunities. In the United States, 72% of high schools offer work-based learning opportunities for credit. This is the first study to describe school performance and school-based behaviors among students enrolled in STW programs and compare them with nonworking and other-working students. Methods In 2003, a questionnaire was administered to five school districts and one large urban school in Wisconsin. Between 2008 and 2010, analyses were completed to characterize STW students and compare them with other students. Results Of the 6,519 students aged 14-18 years included in the analyses, 461 were involved in an STW program (7%), 3,108 were non-working (48%), and 2,950 were other-working students (45%). Compared with other students, STW students were less likely to have a grade point average >2.0, more likely to have three or more unexcused absences from school, and more likely to spend <1 hour in school-sponsored activities. Holding multiple jobs also negatively affected a student's academic performance. Conclusions School-to-Work students reported poorer academic performance and more unhealthy school-related behaviors compared with nonworking students and other-working students. Whereas many factors have a role in why students perform poorly in school, more research on students enrolled in STW programs is needed to understand whether participating has a negative impact on students' academic achievement. © 2014 Society for Adolescent Health and Medicine. All rights reserved.