We　report　herein　the　synthesis　of　two　different　silver　clusters　of　aryl-　and　alkyl-thiolates.　These　two　cluster　complexes　exhibited　biased　C-S　bond　cleavage　reaction　rates　upon　removing　protective　hexamethylazacalix[6]pyridine　(Py[6])　ligands,　which　was　applied　in　the　fabrication　of　silver　sulfide　nanoclusters　with　variable　and　controllable　sizes.