Although there have been various attempts to identify the perceptual-cognitive mechanisms underlying the superior performance of skilled players over novices in sports, few studies have examined the relationship between mental representations and cognitive performance according to the skill levels of players. The purpose of this study was to investigate the functional link between mental representations in long-term memory and cognitive information processing ability in working memory by analyzing mental representation structure and cognitive performance according to skill level. Twenty male skilled and 25 male novice tennis players participated in this study. Structural dimensional analysis of mental representation was used to evaluate the mental representation structure of a tennis serve. In addition, cognition and movement chronometry was used to assess the cognitive performance of a tennis serve in working memory. Results of the representational analysis showed that the similarity of the skilled players to the standard representation structure was higher than that of novices. Furthermore, results in cognitive performance showed that the skilled players had a higher accuracy and shorter response time compared to the novices. Finally, a significant correlation between the adjusted Rand index and cognition movement chronometry accuracy was observed. Taken together, the mental representation structure and cognitive performance of the skilled players were superior to those of the novices, and mental representations were positively correlated with the accuracy of the cognitive information processing. These results imply that the degree of functional connection between working memory and long-term memory may be used as a perceptual-cognitive factor to explain improvement in performance.