Volition is described as a psychological construct with great emphasis on the sense of agency. During volitional behavior, an individual always presents a volitional quality, an intrapersonal trait for dealing with adverse circumstances, which determines the individual's persistence of action toward their intentions or goals. Elite athletes are a group of experts with superior volitional quality and, thereby, could be regarded as the natural subject pool to investigate this mental trait. The purpose of this study was to examine brain morphometric characteristics associated with volitional quality by using magnetic resonance imaging (MRI) and the Scale of Volitional Quality. We recruited 16 national-level athletes engaged in short track speed skating and 18 healthy controls matched with age and gender. A comparison of a parcel-wise brain anatomical characteristics of the healthy controls with those of the elite athletes revealed three regions with significantly increased cortical thickness in the athlete group. These regions included the left precuneus, the left inferior parietal lobe, and the right superior frontal lobe, which are the core brain regions involved in the sense of agency. The mean cortical thickness of the left inferior parietal lobe was significantly correlated with the independence of volitional quality (a mental trait that characterizes one's intendency to control his/her own behavior and make decisions by applying internal standards and/or objective criteria). These findings suggest that sports training is an ideal model for better understanding the neural mechanisms of volitional behavior in the human brain.