Neurofeedback (NFB) involves a brain-computer interface that allows users to learn to voluntarily control their cortical oscillations, reflected in the electroencephalogram (EEG). Although NFB is being pioneered as a noninvasive tool for treating brain disorders, there is insufficient evidence on the mechanism of its impact on brain function. Furthermore, the dominant rhythm of the human brain is the alpha oscillation (8-12Hz), yet its behavioral significance remains multifaceted and largely correlative. In this study with 34 healthy participants, we examined whether during the performance of an attentional task, the functional connectivity of distinct fMRI networks would be plastically altered after a 30-min session of voluntary reduction of alpha rhythm (n=17) versus a sham-feedback condition (n=17). We reveal that compared to sham-feedback, NFB induced an increase of connectivity within the salience network (dorsal anterior cingulate focus), which was detectable 30min after termination of training. This increase in connectivity was negatively correlated with changes in 'on-task' mind-wandering as well as resting state alpha rhythm. Crucially, there was a causal dependence between alpha rhythm modulations during NFB and at subsequent resting state, not exhibited by the SHAM group. Our findings provide neurobehavioral evidence for a temporally direct, plastic impact of NFB on a key cognitive control network of the brain, suggesting a promising basis for its use to treat cognitive disorders under physiological conditions.