The current understanding of high intellectual ability (HIA) involves considering the multidimensional nature of the skills that comprise it. In addition, conceptual advances related to how individuals manage the high intellectual resources available to them may help explain the possible gap between performance and high levels of competence. Understanding the role of executive functioning and metacognition in relation to the management of these resources is essential. Nonetheless, to date, the trajectory of their study is diverse, and empirical and measured evidence in this regard is limited. Thus, the objective of this work was to understand the relationship between executive functions and metacognition (and its components), as well as the measurement of these factors and their reliability. The study sample comprised schoolchildren (n = 43) with an HIA and a control group (n = 46) of schoolchildren with typical intelligence levels. Network analysis revealed differential intergroup connections between the executive functioning components as well as between those of metacognition and for each construct. The greatest relational weight was for metacognition components, with the most robust relationship being found in the group with HIA with metacognitive regulation, flexibility, and verbal working memory versus metacognitive awareness and inhibition in the typical group. Measurement derivations and their application in educational interventions to optimise the expression of high potential are also discussed.