Real-world networks typically exhibit several aspects, or layers, of interactions among their nodes. By permuting the role of the nodes and the layers, we establish a new criterion to construct the dual of a network. This approach allows to examine connectivity from either a node-centric or layer-centric viewpoint. Through rigorous analytical methods and extensive simulations, we demonstrate that nodewise and layerwise connectivity measure different but related aspects of the same system. Leveraging node-layer duality provides complementary insights, enabling a deeper comprehension of diverse networks across social science, technology and biology. Taken together, these findings reveal previously unappreciated features of complex systems and provide a fresh tool for delving into their structure and dynamics.