We report the synthesis and crystal structure determination of two novel chiral gold nanoclusters. By utilizing BINAP, we isolate atomically precise intrinsically chiral Au nanoclusters [Au-9(R-/S-BINAP)(4)](CF3COO)(3) and [Au-10(R-/S-BINAP)(4)(p-CF3C6H4C C)](CF3COO)(3) in high yield with one-pot synthesis. Aug has C-2 geometry, while Au-10 is C-1 symmetric. Interestingly, reversible interconversion between Au-9 and Au-10 can be realized by the addition or removal of a RC CAu component. The transformation from Au-9 to Au-10 leads to significant enhancement of CD signals. The maximum anisotropy factor in the visible region of [Au-10(BINAP)(4)(p-CF3C6H4C C)](3+) is the hitherto largest (up to 6.6 x 10(-3)) among gold nanoclusters, which is approximately twice of that of [Au-9(BINAP)(4)](3+). This work demonstrates that the chiroptical activity of gold nanoclusters can be modulated by structural control through the introduction of second ligands.