OpenCourseWare (OCW) has been rapidly applied to various countries. However, many OCW users do not have enough learning motivations and some even dropped out in the middle. This study intended to investigate the factors that influence the user intention of using OCW and purposed a theoretical framework named the Theory of User Acceptance of OCW. Questionnaire survey was done to analyze the relationships among external variables, intermediate variables, and dependent variables within the theory. Correlation and multiple regression analyses were done to verify the research hypotheses. The results indicated that in terms of using OCW, the knowledge and experience influences the behavioral attitude; the effect of organization and community influences the subjective norm; and channels to elevate computer literacy influences perceived behavioral control. Moreover, the behavioral attitude, the subjective norm, and perceived behavioral control all influence the user intention. These conclusions also provide validations to the purposed theoretical framework.