Plasmonic manipulation using well-designed triangular trimeric gold nanostructures achieves a giant (greater than 50%) crystal enantiomeric excess (CEE) of sodium chlorate (NaClO3). Stronger asymmetric interactions between molecule and light are pursued to reach high enantiomeric excess. The well-designed gold nanostructures immersed in a saturated NaClO3 D2O solution were irradiated with linear, left-hand, and right-hand circular polarizations of a 1064 nm continuous-wave laser. Within seconds of the start of the irradiation, an achiral metastable crystal was formed at the laser focus, and further irradiation induced a subsequent polymorphic transition to the chiral crystal. The crystal chirality is sensitive to the handedness of circular polarization, allowing for efficient enantioselectivity. The mechanisms to achieve this giant CEE are proposed based on the results of electromagnetic field analysis generated near the nanostructure by the finite element method.