This study explores the process of adoption of new information technologies by the users of rural tourism services and, more concretely, the underlying psychological factors of individuals that explain their intentions to make bookings or reservations directly through the websites of the rural accommodations (online purchase intentions). Based on the Unified Theory of Acceptance and Use of Technology (UTAUT), this study establishes a theoretical model that includes five explanatory variables of the online purchase intention: performance expectancy, effort expectancy, social influence, facilitating conditions, and innovativeness. The empirical results obtained in a sample of 1083 tourists that had previously visited several websites of rural accommodations suggest that the online purchase intention is positively influenced by: 1) the levels of performance and effort expected with regard to the transaction; and 2) the level of innovativeness of users. In addition, the innovativeness construct has a moderating effect on the relationship between performance expectancy and online purchase intention.