The columnar polarization direction of ferroelectric columnar liquid crystals can be switched by applying an external electric field, and the polarization direction can be maintained, even after the electric field is removed. If the polarization direction of each column in ferroelectric columnar liquid crystals can be switched and maintained, then ultrahigh-density memory devices can be generated. Recently, we found that the columnar phase of N,N'-bis(3,4,5-tri(S)-citronellyloxyphenyl)urea (Urea-(S)-cit) shows ferroelectricity, whereas that of N,N'-bis(3,4,5-tridecyloxyphenyl)urea (Urea-10) does not. However, the mechanisms by which the six chiral alkoxy groups in Urea-(S)-cit generate ferroelectricity have not been determined. In this study, we regioselectively synthesized four diphenylurea compounds containing (S)-citronellyloxy and decyloxy groups, i.e., N,N'-bis(3,5-di((S)-citronellyloxy)-4-decyloxyphenyl)urea (1), N,N'-bis(4-((S)-citronellyloxy)-3,5-didecyloxyphenyl)urea (2), N,N'-bis(3-((S)-citronellyloxy)-4,5-didecyloxyphenyl)urea (3), and N,N'-bis(3,4-di((S)-citronellyloxy)-5-decyloxyphenyl)urea (4), and investigated which chiral alkoxy group at which position is strongly responsible for the ferroelectricity. The chiral alkoxy groups at 3- and 5-positions of the phenyl groups were clarified to play a significant role in the generation of ferroelectricity. Furthermore, a comparison of these four compounds based on circular dichroism spectroscopy and second harmonic generation experiments revealed the relationship between the helical structure order and the stability of the polarized structure.