This study investigates the relationships among digital competence, attitudes toward artificial intelligence, and digital work readiness among e-commerce students in Thai Nguyen University of Information and Communication Technology grounded in the European Commission’s DigComp 2.1 framework and the Theory of Planned Behavior (TPB). The research analyzes survey data from 270 students using scale validation, Exploratory Factor Analysis (EFA), Confirmatory Factor Analysis (CFA), and Structural Equation Modeling (SEM). The findings reveal that all five dimensions of digital competence, information and data literacy, digital communication, content creation, digital safety, and problem-solving positively influence students’ attitudes toward AI. Among these, digital safety and information processing exert the strongest effects. Notably, attitudes toward AI play a key mediating role, explaining up to 78.2% of the variance in digital work readiness. The study contributes to both theory and practice by emphasizing the importance of integrating artificial intelligence-related content and digital competence development into higher education curricula to better prepare students for the digital workforce.