The synthesis of monodisperse gigantocycles with 63, 87, and 147 ring atoms on the gram scale is described. These molecules were assembled from terphenylene derivatives and long, flexible chains which were mainly aliphatic, with terminal alkyne groups. The latter allowed for ring formation through oxidative alkyne dimerization in high yield (80-87%). The combination of a rod-like and a banana-shaped mesogen connected by flexible chains within the backbone of a ring gives rise to nematic and smectic mesophases.