Genetic effects on academic achievement are likely to capture environmental, developmental, and psychological processes. How these processes contribute to translating genetic dispositions into observed academic achievement remains critically under-investigated. Here, we examined the role of non-cognitive skills-e.g., motivation, attitudes and self-regulation-in mediating education-associated genetic effects on academic achievement across development. Data were collected from 5,016 children enrolled in the Twins Early Development Study at ages 7, 9, 12, and 16, as well as their parents and teachers. We found that non-cognitive skills mediated polygenic score effects on academic achievement across development, and longitudinally, accounting for up to 64% of the total effects. Within-family analyses highlighted the contribution of non-cognitive skills beyond genetic, environmental and demographic factors that are shared between siblings, accounting for up to 83% of the total mediation effect, likely reflecting evocative/active gene-environment correlation. Our results underscore the role of non-cognitive skills in academic development in how children evoke and select experiences that align with their genetic propensity.