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Compounds <jats:bold>[5]HA2N<\/jats:bold> and <jats:bold>[7]HA<\/jats:bold> consisting of 19 and 21 benzene rings, respectively, were synthesized by fourfold cycloisomerization of the corresponding terminal alkyne precursors. The helical structures were confirmed by X\u2010ray crystallographic analysis, where the aromatic frameworks stacked effectively with the helical turn numbers exceeding two. The enantiomers of the two compounds were resolved by chiral HPLC. Whereas <jats:bold>[5]HA2N<\/jats:bold> readily underwent enantiomerization at room temperature at the barrier to enantiomerization of 91\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup>, the barrier was enhanced to 99\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup> for the long analog <jats:bold>[7]HA<\/jats:bold>. The enantiomers of <jats:bold>[7]HA<\/jats:bold> exhibited strong responses in the circular dichroism (CD) and circularly polarized luminescence (CPL) spectra, as scaled by dissymmetry factors |<jats:italic>g<\/jats:italic><jats:sub>abs<\/jats:sub>|=0.034 and |<jats:italic>g<\/jats:italic><jats:sub>lum<\/jats:sub>|=0.012. Theoretical calculations by the r<jats:sup>2<\/jats:sup>SCAN\u20103c method suggested stepwise mechanisms for the enantiomerization via helical inversion with acceptable barrier heights. 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