Empathic capacity has been shown to be correlated with brain structural variations, such as cortical thickness. Since psychotherapists have a constant demand to modulate their empathic response, in this study we compared cortical thickness between a group of psychotherapists and a control group at prefrontal and cingulate brain regions, and investigated how this is correlated with their empathic skills. Eighteen psychotherapists and eighteen healthy controls underwent 3-Tesla MRI scanning and completed empathy-related psychometric assessments. Cortical thickness (CT) measures were estimated for each participant. We evaluated how these measures differed between groups, and if they were associated with individual empathy-related scores in a series of regions of interest. Our analysis shows that psychotherapists display a significantly greater CT at a region in the left dorsolateral prefrontal cortex (dlPFC; p < 0.05, FDR corrected). Moreover, psychotherapists’ CT in this region is correlated with the tendency to feel empathically concerned for others (p < 0.01, FDR corrected). This finding is relevant because the dlPFC region participates strongly in the cognitive components of the empathic response, such as emotion regulation and perspective-taking processes. Thus, our findings support the idea that empathic capacity is reflected by brain structural variations while also studying for the first time a sample of subjects for whom empathic responding is crucial in their profession.