Solid-state 13C NMR measurements were made for the B2 and B4 phases of the achiral banana-shaped molecule, P-14-O-PIMB, which exhibits a direct transformation from the B2 phase to the B4 phase. In both phases, an NMR resonance signal assigned to carbonyl carbons of the ester linkages appears as doublet peaks, showing that the two carbonyl carbons are circumstanced in different electronic environments on the NMR time scale. The chemical shifts of the two peaks are 165.6 and 163.9 ppm in the B2 phase, and these values are not changed in the transformation to the low-temperature B4 phase. To explain this distinct splitting of the carbonyl carbon signal, we take three assumptions into account:  (1) the molecules are accommodated in the unique phase, but the conformational exchange between two states takes place slowly; (2) the two side wings of each molecule experience fast interconformational jumps, but their “average conformer” is different, thus giving two different peaks in the spectra; and (3) the individual molecule claims the twisted conformation, where the two carbonyl carbons of the ester moieties are twisted away from each other by rotating out of the molecular core plane with different dihedral angles. From the present 13C NMR results, the first and second possibilities are ruled out, and it is concluded that the banana-shaped molecules assume the twisted conformation, which is attributable to the origin of the chirality of the B2 and B4 phases in the achiral banana-shaped molecular system.