This study probes the mechanism of artificial intelligence’s (AI’s) influence on Chinese college students’ willingness to participate in online politics and constructs a theoretical model based on the theory of planned behavior. Through the analysis of questionnaire data acquired from up to 317 Chinese college students in total, it turns out that the use of AI affects Chinese college students’ willingness to the participation of online political practice significantly and positively, and such online political participation cognition of Chinese college students plays a mediating role, three aspects of which included as the followings on behavioral attitudes, subjective norms, and perceived behavioral control. Additionly, media literacy level plays a moderating role in online political participation cognition and willingness to participate. All the findings highlight the importance of optimizing the online political participation environment, enhancing college students’ cognition of political participation, and improving media literacy in the context of the digital era, which provides practical guidance for promoting healthy and positive online political participation among college students.