The recently discovered orthorhombic liquid crystal (LC) phase of symmetry Fddd is proving to be widespread. In this work, a chiral hydroxybutyrate linkage is inserted into the molecular core of hexacatenar rodlike compounds, containing a thienylfluorenone fluorophore. In addition to more usual tools, the methods used include grazing-incidence X-ray scattering, modulated differential scanning calorimetry (DSC), flash DSC with rates up to 6000 K/s, and chiro-optical spectroscopies using Mueller matrix method, plus conformational mapping. Although pure R and S enantiomers form only a strongly chiral hexagonal columnar LC phase (Colh*), the racemic mixture forms a highly ordered Fddd phase with 4 right- and 4 left-handed twisted ribbon-like columns traversing its large unit cell. In that structure, the two enantiomers locally deracemize and self-sort into the columns of their preferred chirality. The twisted ribbons in Fddd, with a 7.54 nm pitch, consist of stacked rafts, each containing ∼2 side-by-side molecules, the successive rafts rotated by 17°. In contrast, an analogous achiral compound forms only the columnar phase. The multiple methods used gave a comprehensive picture and helped in-depth understanding not only of the Fddd phase but also of the "parachiral" Colh* in pure enantiomers with irregular helicity, whose chirality is compared to the magnetization of a paramagnet in a field. Unusual short-range ordering effects are also described. An explanation of these phenomena is proposed based on conformational analysis. Surprisingly, the isotropic-columnar transition is extremely fast, completing within ∼20 ms. A clear effect of phase on UV-vis absorption and emission is observed.