Students’ conceptions and knowledge of Vocational Education and Training (VET), the world of work, and the changing nature of work are fundamental to the future of the VET sector and the prosperity of the nation. While there has been a proliferation of research on aspirations for university education, relatively little work has been undertaken focusing on students’ aspirations for VET (NSW DEC, 2012). In particular, little is known about the formation of VET aspirations during the school years, despite an increasing body of evidence indicating that aspirations are often well-formed before the usual careers activities of the later high school years (Gore et al., 2015; Whitty et al., 2015). This paper focuses on what students know about vocational pathways and when their interest in VET forms at a level of detail not previously undertaken in the Australian context. Drawing on data from a four-year ARC Linkage Project (2012-2015), we consider when VET begins to feature in students’ thinking about their futures. Surveys and linked data from more than 10,000 NSW students, from across Year 3 to Year 12 are used. Focus group and interview data with students and some of their parents and teachers complement the survey data to enable a unique and complex account of how VET choices take shape and how vocational pathways are perceived. We report on the ways in which barriers and enabling conditions differ for male and female, Aboriginal and non-Aboriginal, and provincial and metropolitan students. Furthermore we report on VET aspirations and factors relating to schooling (such as peer networks, perceptions of school performance, school performance [NAPLAN results]) and family (such as qualifications, employment, social networks, and cultural resources). While both student backgrounds and their schooling matter, the effect of these variables is generally weak. Most students have a plethora of choices and opportunities when it comes to their vocational futures, often supported by their experiences in school and at home. What is lacking is the opportune use of vocational knowledge and experience by the most influential people in students’ lives to provide specific support to help them make choices as they move through school towards work. The findings from this study are central to addressing the disparity between larger systemic aims for building a strong vocational workforce and the vocational desires of school children.