The synthesis and characterization of triynylbenzenes, 1-iodo-2,4,5-tri(4-alkoxyphenylethynyl)benzenes (1), are reported, and their structure–mesomorphism relationship is investigated. These compounds possess a y-shaped geometry with rigid linear spacers and a stable nematic phase that was achieved by lengthening the alkoxy chains or replacing the iodo group with a smaller atom. The low aspect ratios and identified calamitic nature of these rigid y-shaped liquid crystals make them suitable as potential candidates to be used in the liquid crystal layer of liquid crystal display devices for improving viewing angles. In addition, the geometry of 1 was modified stepwise from a rigid y-geometry to a rigid rectangle for realization of the unstable nematic behaviors of the previously reported board-like 1,2,4,5-tetrakis(4-tridecyloxyphenylethynyl)benzene that was expected to potentially show biaxial nematic phases. The sizes of the fourth side-arm and hence the aspect ratios of these tetra-substituted benzenes are ascribed to the less liquid crystallinity.