Diastereomeric alpha- or beta -CF3 liquid crystalline molecules (LCs) with double stereogenic centers are reported as conformational probes for the bent (L-shape) conformation of antiferroelectric LCs. The diastereomeric LCs show their intriguing features that the racemic composition for both diastereomers self-assemble into the enantiomeric domain spontaneously to exhibit the electrooptic switching.