We conducted a study on a local scale targeting the relationship of economic capital, cultural capital, young people's literacy, numeracy achievements, and the school-to-work transition. We investigated whether participation rates by very young children in early childhood education (ECE) may mediate the historical effects of economic and cultural capital. We analysed longitudinal data from a high-quality national database that included information from 103 Italian provinces. We used structural equation modelling (SEM), multi-sample SEM to investigate spatial inequalities, and mediation analyses. Vector Autoregression models were estimated to determine the temporal trend and the relationship occurring between economic capital and ECE. Results indicate that economic capital is associated with young people's literacy and numeracy achievements and with the NEET rate, with only partial mediation played by the rate of participation in ECE. The association of cultural capital on the NEET rate is near to significance, but it is strongly mediated by participation in ECE. Together, these results imply that the rate of participation in ECE in the Italian provinces may mediate the effect of cultural capital, but only partly that of economic capital.