For decades entrepreneurial motivations have been related to entrepreneurial behavior, in areas such as investments or formulation of strategies, however, its link with the adoption of e-commerce in microenterprises has not been explored. Likewise, most of the research on e-commerce has been focused on studying small and medium-sized companies. Consequently, this research aims to assess the relationship of motivations of micro-entrepreneurs when developing their businesses, with the barriers they perceive to adopt the Internet, and the types of e-commerce activities they implement in their companies. In addition, demographic variables are analysed in order to facilitate the categorization of these organizations. Logistic regressions and Chi-square statistics are developed, on data published in the Fifth Micro-Entrepreneurship Survey of Chile. The results obtained show that the motivation for entrepreneurship based on family tradition is related to less Internet adoption and uses for e-commerce; also, it is evidenced that necessity and opportunity-based motivations are positively associated with Internet use for relationship purposes with clients and suppliers. This information is considered relevant in practical terms, since it allows strengthening the use of e-commerce in microenterprises, through the implementation of programs to support microentrepreneurs with incident characteristics, under the financing of governmental entities or private companies.