While a large variety of conjugated polymers exist, polydiacetylenes (PDAs) remain a major research area among scientists due to their interesting optical, spectral, electronic, and structural properties. Heavily reviewed in regards to their stimuli responsive properties, much is known about the assortment of sensing and detection capabilities of PDAs. In this article, we look more upon the structural diversities of polydiacetylenes that have been achieved in recent years, particularly from a hierarchical perspective of 1, 2, and 3-dimensional configurations. In addition, we examine how these different dimensional arrangements of PDAs have heralded clear applications in several key areas. Successful integration of these stimuli-responsive "smart" materials into various geometries has required researchers to have a comprehensive understanding of both the fabrication and synthesis processes, as well as the signalling mechanism for the optical, fluorogenic or spectral transitions. The on-going discovery of new PDA formulations continues to provide interesting structural manifestations such as liposomes, tubes, fibres, organic/inorganic incorporated hybrids and composite structures. By highlighting some of the recent conceptual and technological developments, we hope to provide a measure of the current pace in new PDA derivative development as core components in efficient sensor, imaging and display systems.