The size of cities is known to play a fundamental role in social and economic life. Yet, its relation to the structure of the underlying network of human interactions has not been investigated empirically in detail. In this paper, we map society-wide communication networks to the urban areas of two European countries. We show that both the total number of contacts and the total communication activity grow superlinearly with city population size, according to well-defined scaling relations and resulting from a multiplicative increase that affects most citizens. Perhaps surprisingly, however, the probability that an individual's contacts are also connected with each other remains largely unaffected. These empirical results predict a systematic and scale-invariant acceleration of interaction-based spreading phenomena as cities get bigger, which is numerically confirmed by applying epidemiological models to the studied networks. Our findings should provide a microscopic basis towards understanding the superlinear increase of different socioeconomic quantities with city size, that applies to almost all urban systems and includes, for instance, the creation of new inventions or the prevalence of certain contagious diseases.