Given that there are neural markers for the acquisition of a non-verbal skill, we review evidence of neural markers for the acquisition of vocabulary. Acquiring vocabulary is critical to learning one's native language and to learning other languages. Acquisition requires the ability to link an object concept (meaning) to sound. Is there a region sensitive to vocabulary knowledge? For monolingual English speakers, increased vocabulary knowledge correlates with increased grey matter density in a region of the parietal cortex that is well-located to mediate an association between meaning and sound (the posterior supramarginal gyrus). Further this region also shows sensitivity to acquiring a second language. Relative to monolingual English speakers, Italian–English bilinguals show increased grey matter density in the same region. Differences as well as commonalities might exist in the neural markers for vocabulary where lexical distinctions are also signalled by tone. Relative to monolingual English, Chinese multilingual speakers, like European multilinguals, show increased grey matter density in the parietal region observed previously. However, irrespective of ethnicity, Chinese speakers (both Asian and European) also show highly significant increased grey matter density in two right hemisphere regions (the superior temporal gyrus and the inferior frontal gyrus). They also show increased grey matter density in two left hemisphere regions (middle temporal and superior temporal gyrus). Such increases may reflect additional resources required to process tonal distinctions for lexical purposes or to store tonal differences in order to distinguish lexical items. We conclude with a discussion of future lines of enquiry.