This paper describes and discusses the learning potential of work activities and interactions that are deemed to be inherently pedagogically rich, their qualities, and their educational worth. The aim is to illustrate and elaborate the pedagogic qualities of these activities and how their potential can be optimized to assist both students and workers to learn in and through everyday work activities. A key consideration here is that these kinds of potentially rich learning experiences are unlikely to be provided or to be accessible in any other way. Commencing with outlining a series of premises about how learning through work might be understood, the paper progresses by discussing the importance of these kinds of learning experiences that occur as part of everyday work activities. Then, a specific set of five bases are proposed to explain the potency for learning of these kinds of activities, drawing upon conceptual accounts of learning and empirical research into learning through workplaces. These pedagogic qualities are illustrated with examples from healthcare work, as are ways of optimizing their learning potential. It is suggested that beyond what is afforded by these work activities and interactions, just as essential are the bases by which individuals come to engage with them. Without effortful engagement, the potential of those activities and interactions will not be realized. Finally, practices promoting the efficacy of pedagogically rich activities are identified and presented.