This thesis focuses on education and work choices of individuals in both developing and developed economies. Such economic settings are distinguishable partly in terms of the features and constraints underlying individual decision-making, which impact on the disparity in education levels between low- and high-income economies. In particular, low-income settings are characterised by a large degree of poverty, risk and uncertainty in daily life, the effects of which are often exacerbated by a lack of risk diversification mechanisms due to thin insurance markets and high borrowing constraints. These features have important implications for investment in education. The higher levels of investment in education in developed economies are largely due to higher levels of wealth, opportunities and well-functioning institutions including markets for insurance and credit, along with the higher availability and quality of educational institutions. Even so, the severity of constraints right throughout the education lifecycle varies extensively across the income spectrum within developed economies. This is reflected in the lower levels of educational attainment of low-income individuals compared to individuals from richer backgrounds. To begin with, I examine the effects of living in an environment that is inherently risky, on human capital accumulation in Indonesia. I then move on to an analysis of work and education decisions of children in rural Mexico, specifically considering potential interactions between the opportunity costs of education and the sibling composition of the child. Finally, I assess the impact of the Education Maintenance Allowance, a conditional education subsidy, on post-compulsory education and work choices in the UK.