The emergence of the network paradigm has led to growing interest in understanding network structures relating to knowledge flows and patterns of regional innovation. This paper explores the structure of knowledge networks stemming from ties between universities and other actors, principally firms. Based upon a network analysis of empirical data for regions across the UK, it is found that the most innovative and economically developed regions are more likely to be the location for actors holding highly central and influential positions within knowledge network architectures. It is concluded that network structures, and resulting stocks of structural network capital, influence patterns of regional innovation and development.