The concept of Smart Cities is an emerging social and technology innovation, attracting large public and private investments at a global scale, arguing for the effective exploitation of digital technologies to drive quality of living and sustainable growth. However, these investments mainly focus in smart technical infrastructure, and they have yet to be systematically complemented with efforts to prepare the human capital of future smart cities in terms of core competences anticipated for exploiting their potential. In this context, this chapter introduces “cyber-physical learning” as a generic overarching model to cultivate Digital Smart Citizenship competence. The proposed approach exploits the potential of Internet of Things technologies to create authentic blended and augmented learning experiences. Proof-of-concept case studies of the proposed cyber-physical learning approach, to develop smart household energy management competences, are presented and discussed as a field of application. Finally, the findings of a survey with university students for eliciting their attitudes to engage with cyber-physical learning environments for enhancing their digital smart citizenship competences are reported.