When a DMF solution of 1,8,13-trimercaptotriptycene is allowed to stand under an inert atmosphere, a single crystalline molecular cluster with disulfide bonding results. Likewise, several thiol-containing triptycene derivatives yield single crystalline disulfide-containing clusters with different structural patterns. One of these clusters featuring a densely arranged tetrapod-like disulfide moiety exhibits a particularly high refractive index of 1.75, much higher than that of the others, although the sulfur contents of these clusters are comparable.