In recent years, to attract global manufacturers, media reporters, and consumer attention, a popular term in search engines has been virtual reality (VR). In addition to video, entertainment, education, and medical, VR can be used in electronic commerce (E-commerce). Currently, most E-commerce platforms present products using 2D images, text-based interface or animation. However, consumers want to know more about the products while online shopping and compare the product’s material, color, and other elements. Therefore, combining VR with E-commerce can improve the user’s shopping experience. This study will focus on the characteristics of VR and E-commerce. This feature can be used to interactively study UI and UX between users and designers to generate design criteria. Experimental design is carried out through the modified SEM-CPU method. Then, we use the think-aloud protocols, Questionnaire for User Interaction Satisfaction, and User Experience Questionnaire to understand the user’s thoughts on UI and UX. Moreover, this study uses focus group to interview experts to obtain expert opinions on VR E-commerce. Induction and integration of data is carried out to produce design criteria by experimental results. Finally, the Delphi method is utilized to validate and evaluate the practicability of the design criterion. Through the “UI and UX design criteria of VR” generated by this study, many important design elements can be proposed and assessed in VR E-commerce. In closing, this study provides design and development suggestions for VR developers to improve the positive influence of UX.