Internet addiction seriously influences individuals` physical and mental health and social development. Much research has documented that impulsivity is probably a potential neurocognitive marker related to addictive behavior. However, further research is needed to identify the mediating and moderating mechanisms underlying this relation. Based on the polyvagal theory and differential susceptibility model, the present study examined two research questions: (a) the mediating role of smart phone multitasking between college students’ impulsivity and their internet addiction, and (b) the moderating role of cardiac vagal tone played in the relation between impulsivity and college students’ internet addiction. Data were collected from 139 Chinese college students (Mage = 19 years, SD = 1.4) who completed questionnaires regarding internet addiction, impulsivity and smart phone multitasking. Electrocardiogram data were collected and High Frequency Heart Rate Variability (HF-HRV) were computed. The results indicated that after controlling for gender, age and socioeconomic status (a) smart phone multitasking partially mediated the positive association between impulsivity and college students’ internet addiction; and (b) The relationship between college students’ impulsivity and internet addiction depends on their baseline HF-HRV, such that the positive association between impulsivity and college students’ internet addiction were stronger among students with low HF-HRV. The findings of the study indicated that college students’ impulsivity could make them more prone to smart phone multitasking, which further intensify the risk of internet addiction. In addition, the effect of impulsivity on internet addiction was buffered by higher level of baseline HF-HRV indicating the baseline HF-HRV could be a protective factor of impulsive students. Overall, this study verified the interactive contributions of individual characteristic, individual behavioral tendencies and physiological factor on internet addiction, and it has certain guiding significance for the intervention of college student’s internet addiction.