This study focuses on the relationship between personality traits, derived from the Big Five model, and performance in the competitive electronic sports (eSports) video game League of Legends (LoL). Data were gathered from 206 LoL players of various in-game success levels, as measured by their position within the competitive hierarchy (division) of the video game. The NEO-Five Factor Inventory (NEO-FFI) questionnaire was used to measure personality traits within the gathered sample, which was divided into two groups of higher and lower ranked players. The results indicate that players who reach higher divisions in LoL tend to be less extraverted, less agreeable, but more open to experience. This is one of the few reported links between eSports performance and personality traits, in what is still a nascent yet rapidly developing research topic. The results are discussed within the context of available knowledge on personality and traditional competitive sports performance.