Determining relations between brain structure and function is a principal focus of evolutionary neurobiology. Here we investigate covariation between singing behaviour and the neuroanatomy in eight species of sylviid warblers from the closely related Acrocephalus and Locustella genera. We found a significant positive correlation between repertoire size and the volume of the higher vocal centre after controlling for variation in brain size and phylogenetic relatedness across species. This group is of particular interest, as earlier work has shown that an increase in male song complexity (as measured by syllable repertoire size) is caused by sexual selection pressure acting through female choice. Thus, in males of Acrocephalus species (which have complex songs), sexual selection appears to have led to increases in both syllable repertoire size and the relative volume of the higher vocal centre. In contrast, Locustella species have very simple songs, and repertoire size and the relative volume of the higher vocal centre remain small in males of these species. These results indicate that sexual selection may have shaped the evolution of a particular behavioural trait (song) by altering the relevant controlling area of the brain (higher vocal centre).