Chess is a good model to study high-level human brain functions such as spatial cognition, memory, planning, learning and problem solving. Recent studies have demonstrated that non-invasive MRI techniques are valuable for researchers to investigate the underlying neural mechanism of playing chess. For professional chess players (e.g., chess grand masters and masters or GM/Ms), what are the structural and functional alterations due to long-term professional practice, and how these alterations relate to behavior, are largely veiled. Here, we report a multimodal MRI dataset from 29 professional Chinese chess players (most of whom are GM/Ms), and 29 age matched novices. We hope that this dataset will provide researchers with new materials to further explore high-level human brain functions.