The interest in educational and professional aspirations of students transiting to post-secondary education has gained prominence in academic debates and policy agendas internationally. Political interventions for raising aspirations quite often draw on narrow instrumental and rationalistic assumptions of individual decision-making that, as we will argue, do not capture adequately the meanings students attribute to these aspirations. By means of in-depth interviews and combining a critical realist approach to social action with capabilities approach, the paper explores the educational and professional aspirations of students at the end of secondary TVET in Chile. We consider that high educational aspirations of secondary TVET students in Chile need to be understood as a reflexive response to significantly high social inequalities in the country, the precarity of working conditions in a highly liberalised labour market, and the enduring neoliberal tenet of meritocracy. We also argue that understanding aspirations is key to reimagine TVET's roles and purposes at individual, institutional and national levels, towards fairer opportunities for human development.