A　‘passivated　precursor’　approach　is　developed　for　the　efficient　synthesis　and　isolation　of　all-alkynyl-protected　gold　nanoclusters.　Direct　reduction　of　dpa-passivated　precursor　Au-dpa　(Hdpa=2,2’-dipyridylamine)　in　one-pot　under　ambient　conditions　gives　a　series　of　clusters　including　Au22(C≡CR)18　(R=−C6H4−2−F),　Au36(C≡CR)24,　Au44(C≡CR)28,　Au130(C≡CR)50,　and　Au144(C≡CR)60.　These　clusters　can　be　well　separated　via　column　chromatography.　The　overall　isolation　yield　of　this　series　of　clusters　is　40　%　(based　on　gold),　which　is　much　improved　in　comparison　with　previous　approaches.　It　is　notable　that　the　molecular　structure　of　the　giant　cluster　Au130(C≡CR)50　is　revealed,　which　presents　important　information　for　understanding　the　structure　of　the　mysterious　Au130　nanoclusters.　Theoretical　calculations　indicated　Au130(C≡CR)50　has　a　smaller　HOMO-LUMO　gap　than　Au130(S−C6H4−4−CH3)50.　This　facile　and　reliable　synthetic　approach　will　greatly　accelerate　further　studies　on　all-alkynyl-protected　gold　nanoclusters.　©　2024　Wiley-VCH　GmbH.