Dispositional envy is distinguished by definition and neurally from episodic envy. While the neural correlates of episodic envy have been evaluated by specific tasks in previous studies, little is known about the structural neural basis of dispositional envy. In this study, we investigated the structural neural basis of dispositional envy underlying individual differences across two independent samples comprising a total of 100 young healthy adults. Firstly, 73 subjects' data (sample 1) was analyzed, and we assessed the association between regional gray matter volume (rGMV) and dispositional envy using voxel-based morphometry (VBM). Furthermore, we explored the role of emotional intelligence in the association between GMV and dispositional envy. VBM indicated that dispositional envy was positively correlated with GMV in the left dorsolateral prefrontal cortex (DLPFC) and superior temporal gyrus (STG). We also found that emotional intelligence partially mediated the association between DLPFC volume and dispositional envy. These results were replicated in another independent sample (Sample 2, n = 27). These results provide the first evidence that dispositional envy exhibits a structural neural correlation with the DLPFC and STG, and give a neutral explanation for why individuals with high emotional intelligence exhibit less envy.