In this work, the liquid crystal (S)-2-methylbutyl-[4 '-(4 '' -heptyloxyphenyl)-benzoyl-4-oxy-(S)-2-((S)-2 ')-benzoyl)-propionyl)]-propionate (ZLL 7/*) was investigated by means of C-13 NMR spectroscopy. This compound has a very peculiar mesomorphic behavior, showing the following phases: paraelectric SmA, ferroelectric SmC*, antiferroelectric SmC*(A), re-entrant ferroelectric SmC*(re), and ferroelectric hexatic Sm*(HEX). The structural and orientational ordering properties of ZLL 7/* have been determined by exploiting the nuclear chemical shielding properties of C-13. To this aim, solid-state NMR techniques such as CP, SPINAL-64, and SUPER have been used in combination with DFT calculations. The agreement between experimental and in vacuo DFT shielding parameters appears to be satisfactory. The orientational order parameters obtained from the C-13 shielding analysis have been discussed, taking into account different data analysis approaches and comparing them to those previously obtained from an independent H-2 NMR study.