In addition to using common 1i'gands thioli or acetylene ligands) to protect metal nanocinstei,s halogens to also be used to participate in the formation of nanoclusters. In this study, we reported the formation of two new nanoclusters promoted by chlorides released from HAuC14: one [Au1Ag26(SR)18C1] with an icosahedral AitiAgi, kernel, which is surrounded by the shell of Ag24(SR)18 and the special chlorine atom fills the space between the metal core and the metal shell; the other [Au6Ag33(Dppf)2(SR)16 6Cl]+ with the kernel consisted of two icosahedral Au3Ag10 units by sharing one vertex Ag atom; which is Protected by the complicated shell of Ag24(Dppf)2(SR)16C14, two special chlorine atoms also fill the space between the metal core and the metal shell. Thus, both two nanoclusters suggest that the chlorine atoms can exist in the space between the metal kernel and 'out shell, playing a critical role in maintaining the stability of the overall structures. These will deepen thee comprehensive understanding of chlorine in constructing the structures of alloy nanoclusters and will also be helpful in mapping out the new strategies for core shell nanocinstei" synthesis.