Over the last decade, Canada has experienced a substantial increase in the number of individuals participating in post-secondary education (PSE). This trend emphasizes the importance of understanding the pathways leading to PSE enrolment and the competencies that are associated with them. This chapter describes a range of possible education and work outcomes at the age of 21, and the pathways that led to them. It describes the wealth of information that is available in the combination of the PISA and YITS databases. This overview provides a useful context in which to consider the complexity and importance of transitioning to postsecondary education and work. (Contains 12 tables, 3 figures, 1 box and 11 footnotes.) [This research paper was prepared for Human Resources and Skills Development Canada by Tomasz Gluszynski Human Resources and Skills Development Canada and Justin Bayard, Human Resources and Skills Development Canada, as a background paper to the PISA Thematic Report--Pathways to Success.]