A one-dimensional lithium(I) coordination polymer has been characterized by variable-temperature single-crystal X-ray diffraction and differential scanning calorimetry. This compound possesses an anisotropic packing arrangement that, along with a scissor-like or hingelike movement of the pyridyl ligand side arms, results in an extremely rare combination of positive, negative, and zero thermal expansion. Designing such types of materials and understanding the mechanistic details can facilitate the design of new thermoresponsive materials.