We designed a hydrogen-bonding tolane-based molecule with terminal carboxyl and alkylsulfanyl groups in an effort to realize thioether-containing rod-like liquid crystalline materials. The molecule successfully exhibits a stable enantiotropic mesophase, in contrast to non-hydrogen bonding derivatives, including tolane and diphenyldiacetylene. In addition, it shows two remarkable characteristics compared to analogues with alkyl or alkoxy groups. First, the mesophase of the alkylsulfanyl derivative shows strong long-range correlation. Second, the birefringence of the alkylsulfanyl derivative is highly temperature-dependent, achieving a maximum value of 0.36. These remarkable characteristics are believed to be due to the high polarisability of sulfur atoms and S-S contacts. These findings will be helpful for the design of novel sulfur-containing rod-like liquid crystalline materials.