As a novel type of mobile game, addictive behavior has attracted the attention of researchers due to its possible negative impacts on several forms of psychological problems. In this research, we tested the relationship between academic performance, mobile game addiction (MGA), and mobile self-efficacy among undergraduates in Taiwan. An academic model has been suggested from the hypotheses and using a sample of 739 college students by estimating the structural equation modeling. This result discloses that college students are an at-risk swarm for the MGA. We realized that MGA was negatively connected with academic performance and mobile self-efficacy, exhibiting a positive relationship between the latter two. Further analysis on age, place of stay, and the duration of playing mobile games distinction was tested in the trajectories from MGA to these psychological health results, and the results revealed that they were significantly associated with MGA. We also dealt with the limitations and recommended that the authorities immediately regard this, and to complete academic goals, college students should refrain from playing mobile games and participate in other forms of healthy entertainment.