A brief overview of structural and functional brain characteristics related to g is presented in the light of major neurobiological theories of intelligence: Neural Efficiency, P-FIT and Multiple-Demand system. These theories provide a framework to discuss the main objective of the paper: what is the relationship between individual alpha frequency (IAF) and g? Three studies were conducted in order to investigate this relationship: two correlational studies and a third study in which we experimentally induced changes in IAF by means of transcranial alternating current stimulation (tACS). (1) In a large scale study (n = 417), no significant correlations between IAF and IQ were observed. However, in males IAF positively correlated with mental rotation and shape manipulation and with an attentional focus on detail. (2) The second study showed sex-specific correlations between IAF (obtained during task performance) and scope of attention in males and between IAF and reaction time in females. (3) In the third study, individuals’ IAF was increased with tACS. The induced changes in IAF had a disrupting effect on male performance on Raven’s matrices, whereas a mild positive effect was observed for females. Neuro-electric activity after verum tACS showed increased desynchronization in the upper alpha band and dissociation between fronto-parietal and right temporal brain areas during performance on Raven’s matrices. The results are discussed in the light of gender differences in brain structure and activity.