In this paper, we present C13 and H1 NMR investigations of 2, 3, 6, 7, 10, 11-hexahexyl-thiotriphenylene (HHTT). The measurements were carried out under both static and magic-angle spinning conditions. The phase diagram of HHTT is K↔H↔ Dhd↔I, where H is a helical phase and Dhd is a columnar liquid crystal. The motivation was to characterize the molecular order and dynamics and to investigate differences at the molecular level between the two mesophases: H and Dhd. It is shown that Dhd is a conventional columnar liquid crystal, where the molecular core undergoes fast rotation about the symmetry axis. The orientational order in this mesophase is lower and the temperature dependence of the order parameter is steeper than in other triphenylene-based compounds. On the other hand, in the helical phase the core, similarly to the solid phase, is essentially rigid. The difference between the solid and helical phases is mainly manifested in an increased mobility of the aliphatic chains observed in the latter phase. In addition, the sample exhibits thermal history effects, which are observed in the different behavior upon cooling and heating.