It is well established that domain general networks (DGNs) in the human brain become active when diverse novel skills and behaviors are being learnt. However, their causal role in learning remains to be established. In the present study, we first performed functional magnetic resonance imaging on healthy participants to confirm that DGNs were most active in the initial stages of learning a novel vocabulary, consisting of pronounceable nonwords (pseudowords), each associated with a picture of a real object. We then examined, in healthy participants, whether repetitive transcranial magnetic stimulation of a frontal midline node of the cingulo-opercular DGN affected learning rates during the initial stages of learning. We report that stimulation of this node, but not a control brain region, substantially improved both accuracy and response times during the earliest stage of learning pseudowords-object associations. This stimulation had no effect on the processing of established vocabulary, tested by the accuracy and response times when participants decided whether a real word was accurately paired with a picture of an object. These results provide evidence that non-invasive stimulation to DGN nodes can enhance learning rates, thereby demonstrating their causal role in the learning process. We propose that this causal role makes DGNs candidate targets for experimental therapeutics; for example, in stroke patients with aphasia attempting to reacquire a vocabulary.