The focus of this research is networked learning within European trade union organisations where there is a strong recognition that technology has a key role to play in developing educational opportunities and in extending the trade union influence locally, nationally and globally. This cross-disciplinary study explores a range of theories, models and approaches which underpin the pedagogical process in a distinctive educational environment, drawing on the fields of learning technology and knowledge management. The development and implementation of two transnational projects on networked learning form the basis of the research. Structuration theory, which highlights the interplay between the objective nature of broader social structures and the subjective perspectives of human agency, provides the epistemological foundation. To balance this highly abstract concept, related theoretical frameworks derived from education, learning technology and social informatics research have also usefully informed the investigations. This study contends that the design of networked learning and preparation for key roles can be valuably informed by focusing on the individual, social and technical boundary encounters inherent in the complex interplay of structure and agency. It has cast new light on an under-researched area of adult education and has highlighted the value of cross-disciplinary collaboration in advancing our understanding of networked learning. It has also gone some way towards addressing the recognised imbalance in linking theory and practice in networked learning and signposts new directions for learning technology research. Most importantly, there is evidence that it has influenced practice in the field, thus fulfilling one of the key aims of the research.