In several fields, the need for a joint analysis of brain activity and eye activity to investigate the association between brain mechanisms and manifest behavior has been felt. In this work, two levels of attentional demand, elicited through a conjunction search task, have been modelled in terms of eye blinks, brain activity, and brain network features. Moreover, the association between endogenous neural mechanisms underlying attentional demand and eye blinks, without imposing a time-locked structure to the analysis, has been investigated. The analysis revealed statistically significant spatial and spectral modulations of the recorded brain activity according to the different levels of attentional demand, and a significant reduction in the number of eye blinks when a higher amount of attentional investment was required. Besides, the integration of information coming from high-density electroencephalography (EEG), brain source localization, and connectivity estimation allowed us to merge spectral and causal information between brain areas, characterizing a comprehensive model of neurophysiological processes behind attentional demand. The analysis of the association between eye and brain-related parameters revealed a statistically significant high correlation (R > 0.7) of eye blink rate with anterofrontal brain activity at 8 Hz, centroparietal brain activity at 12 Hz, and a significant moderate correlation with the participation of right Intra Parietal Sulcus in alpha band (R = −0.62). Due to these findings, this work suggests the possibility of using eye blinks measured from one sensor placed on the forehead as an unobtrusive measure correlating with neural mechanisms underpinning attentional demand.