Esports have grown to become a core part of popular culture in many countries, including Hong Kong. Albeit the low participation rates in Esports in Hong Kong, it was starting to gain traction, yet the local Esports advocates were experiencing challenges in promoting and popularizing the Esport. Hence, the current study was aimed to identify and reveal the determinants of participating in Esports, as well as strengthen the work on Esports behaviors using the theory of planned behavior (TPB), a reliable and valid prominent theory in predicting human behavior across a plethora of contexts, ranging from health-related behaviors to sport consumption behaviors. In the current study, the convenience sampling method was used to recruit over 2000 students (secondary school, N = 1567 (female = 615); university students, N = 1525 (female = 255). The students were invited to participate in the survey for collecting their perception on Esports participation using TPB-based questionnaire. Results were analyzed using theoretical analysis and structural equation modeling (SEM). The results show that both secondary school and university students have positive attitudes toward Esports. The outcomes indicated that participating in Esports develops social networks, and people with professional Esports’ skills capability and being fortitude tend to be models of Esports participation. However, inadequate resources are a significant barrier to participation in the Esports business. The SEM model verified that the variables of intention in Esports participation among the students in Hong Kong with an adequate goodness of fit index. As a whole, the current study has identified the factors and determinants of Esports’ intention and behavior among Hong Kong students, which were successfully displayed in terms of the theory of planned behavior. In addition, the findings are expected to provide the Hong Kong government with a documented framework to advocate Esports-related policies on a long-term basis.