This study examined the relationships between executive functions (EF) and the ability to learn problem-solving principles. It was hypothesized that there are distinct executive domains of attentional control (involving inhibition and selective attention) and cognitive flexibility (working memory and shifting) that predict the ability to learn. Nine to ten year-old children completed a battery of nine tests to provide for multiple-indicator measurement of latent variables. Several alternative models were subjected to structural equation modeling. A three-factor EF structure involving inhibition, selective attention and working memory provided the best fit to the data. Shifting did not emerge as a separate factor and proved to be indistinguishable from working memory. Results indicate a full mediation of inhibition and selective attention effects on the ability to learn via working memory. After controlling for working memory, the paths from inhibition and selective attention to the ability to learn were no longer significant, while working memory accounted for most of the variation in the ability to learn. The findings provide necessary evidence for the hypothesis of a hierarchical structure of EF, where lower-order functions like inhibition and selective attention seem to constitute higher-order functions like working memory which directly determines the efficiency of acquiring novel forms of thinking.