Being proficient in several foreign languages is an essential part of every-day life. In contrast to childhood, learning a new language can be highly challenging for adults. The present study aims at investigating neural mechanisms supporting very initial foreign language learning in adulthood. For this reason, subjects underwent an implicit semantic associative training in which they had to learn new pseudoword-picture pairings. Learning success was measured via a recognition experiment presenting learned versus new pseudoword-picture pairings. Neural correlates were assessed by an innovative multi-methodological approach simultaneously applying electroencephalography (EEG) and functional near-infrared spectroscopy (fNIRS). Results indicate memory-related processes based on familiarity and mechanisms of cognitive control to be present during initial vocabulary learning. Findings underline the fascinating plasticity of the adult brain during foreign language learning, even after a short semantic training of only 18 minutes as well as the importance of comparing evidence from different neuroscientific methods and behavioral data.