Previous studies showed that the onset age of second language acquisition (AoA-L2) can modulate brain structure of bilinguals. However, the underlying mechanism of anatomical plasticity induced by AoA-L2 is still a question in debate. In order to explore the issue, we recruited two groups of native Cantonese-Mandarin speakers, the early group began to speak in Mandarin at about 3.5 and the late group at about 6.5 years old. In addition, the early group had earlier experience in reading Chinese characters than the late group did. Through estimating the cortical thickness (CT), we found that (1) compared with the late group, the early group had thicker CT in the lateral occipital region, left middle temporal gyrus, and left parahippocampal region, which are all involved in visuospatial processing, probably reflecting the effect induced by the earlier or later experiences in processing the characters of Chinese for the two groups; and (2) compared with the late group, the early group had thicker CT in left superior parietal region, which is believed to be involved in language switching, maybe for the early group had the earlier experience in switching back and forth between Cantonese and Mandarin and therefore recruited the executive control network earlier. Our findings revealed the effects of the AoA-L2 in oral language acquisition as well as in written language acquisition as the main determinants of bilingual language structural representation in human brain.