The construction and investigation of photoresponsive and redox-active supramolecular systems with acetylenyl (polyyne) and cumulenic sp hybridized carbon chains (Cn) are reported here. Novel types of one-dimensional rigid molecular rods and macrocyclic molecular squares with controllable and yet fixed chain lengths or cavity sizes are explored. Such systems will have the desired features such as synthetic accessibility, coordination versatility, rigidity, directionality, photostability, electronic conductivity, controllable distances between donors and acceptors, and controllable cavity sizes in macrocyclic molecular squares. These features are extremely important to the future applications of these new rigid supramolecular systems in molecular photonic and electronic devices, light-energy conversion, molecular recognition, and host-guest chemistry.