This work investigated the nanoconfinement effect on the molecular dynamics and phase transition of confined benzene inside titanate nanotubes with a uniform inner diameter of approximately 5.3 nm. For 13C-enriched organics, the 13C nuclear spin-spin relaxation was demonstrated as a sensitive tool to differentiate molecular translational motion and reorientation and, thus, was shown to be advantageous over the commonly employed 1H and 2H NMR for studying complex phase diagram, specifically, for separating the phase behavior of translational motion and the phase behavior of molecular reorientation. In such an approach, the melting of translational motion of confined benzene was explicitly observed to take place in a broad temperature range below the bulk melting temperature. The abrupt change of the 13C nuclear spin-spin relaxation time of the confined liquid benzene at about 260 K suggested that nanoconfinement induced two topologically distinct liquid phases.