An important issue of Internet self-efficacy related to learning performance has been emphasized currently. For college students who attended to a first-time offered online learning, their learning motivational characteristics were expected to play as a critical role to complete the course in a fashion of self-directed instruction. In this present study, the relationships between Internet self-efficacy and learning motivational characteristics were examined in relation to students' learning performance. Participants were 20 college students who fulfilled the class requirements. Data for Internet self-efficacy and learning motivational characteristics were collected by self-reported questionnaires in the beginning of and at the end of the semester. The results showed that Internet self-efficacy measured at the end of the semester was lower that that measured at the onset of the semester, with the former was predictive of learning performance tentatively. Although Internet self-efficacy was not as influential as expected, similar patterns were found in student's gender and the school year of as well. That is, Internet self-efficacy of females and juniors has been reduced downward to a significant level. In the meantime, with regarding to the ARCS model, motivational characteristics of the attention and confidence categories derived from the model were predictive of learning performance in opposite directions. Internet self-efficacy, learning motivational characteristics as well as other important determinants for the success in online learning tend to be explored further in the following studies. In the future, personal factors and situational factors need to be identified. Limitations and suggestions were discussed for later research.