Recently, increased attention has been directed to the brain to better understand how motor skill expertise develops. One promising technique purported to accelerate motor skill improvement is transcranial direct current stimulation (tDCS). While simple fine motor tasks involving the hands and fingers are most frequently used to investigate the role of tDCS on motor skill learning, less work has examined the role of tDCS on complex sensori-motor tasks applicable to occupational, sport, and daily living activities. Esports require a high degree of sensori-motor control and have become one of the most popular forms of digital entertainment worldwide. Currently, no research has quantified the development of motor skill expertise in esports or whether tDCS can enhance skill improvement. The current study aimed to first differentiate the sensorimotor performance of a key gameplay skill among esports players of different skill levels. Secondly, we quantified the training effect on performance. Finally, we investigated the effect of tDCS on performance improvements. We hypothesized that esport players would perform superiorly compared to novice gamers, that all groups would be able to improve their performance through training, and that tDCS would enhance training induced performance improvements. We found that performance on a single fundamental esport skill can differentiate expertise among novice and skilled players, that training can significantly improve performance among all expertise levels and that tDCS preferentially accelerates the performance improvements of novice players. The implications of this work, specifically regarding the temporal application of tDCS during complex motor skill learning and rehabilitation, are discussed.