The purpose of the present article is to outline and illustrate an analytical approach that accentuates the biographically complex processes inhering within early school leaving transitions. The organizing device of 'structural option' (Stones, 2001) is introduced, which brings into focus the role and interplay of types of 'structures' (in a structurationist sense) in the decision-making processes underlying school exit. 'Structural option' combines two important dimensions in influencing young people's choices: cognitive/emotional and relational/interactional structures. This study shows that disengagement from school is more than a straightforward reading that might suggest lack of positive disposition towards education, but rather is born out of powerful interactions across these two main structural dimensions. As an analytical construct, structural options alert us to the importance of analyzing young people's disengagements from mainstream school in terms of social relationships, power, and emotions. While the article is based on empirical findings from an Irish context, the intention is that its scope extends more broadly to qualitative data analysis of school exit transitions within other contextual settings. The empirical focus derives from the interview narratives with fourteen participants attending a second chance educational initiative in Ireland, known as the Youthreach programme. While most of the young people occupy the status of 'early school leaver', closer inspection of their structural options shows that their pathways to early school exit and school disengagement (for those who completed) comprise quite differing structural combinations. As researchers, appreciation of such combinations can help us understand the justifications young people use in their decision-making.