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Complex business patterns from providers and diverse needs of customers in E-commerce necessitate constant and rapid modifications of services for new business models. The online-to-offline (O2O) business model is one of newly developed models where smartphones, tablets, e-readers and digital signages provide mobility and entertainment that ordinary people have never experienced before. Business opportunities are brought forth by O2O from cyberspace into daily reality. User experience (UX) evaluation is thus getting more and more important for user-centered design. In the literature, UX evaluation methodologies were designed for usability and satisfaction of computers or consumer electronics. Their results, however, did not necessarily help design O2O smart business services in that UX constructs in O2O should differ from that in using computers or consumer electronics. Important constructs of UX in O2O such as usability, utility, adoptability and desirability should be considered in the design of service flows and activities. The current study proposed important UX constructs for assessing O2O design by analyzing O2O users. A rapid evaluation method for UX in O2O can be developed based on the constructs.