A　series　of　gold　(I)　phoshpine　complexes　with　diverse　alkynyl　ligands　[Au(C≡CR)(PTA)]　(R=C6H11OH,　1;　C5H9OH,　2;　C15H11OH,　3;　C19H27O2,　4;　C18H23O2,　5;　C9H12N,　6;　CH2OCH2C6H5,　7;　C6H4OCH3,　8;　PTA=1,3,5-Triaza-7-phosphaadamantane)　have　been　synthesized　and　characterized　using　a　range　of　spectroscopic　techniques.　Complex　1　and　3　show　an　infinite　one–dimensional　S–type　and　zigzag　aurophilic　chain,　respectively,　whereas　complex　2　containing　1-ethynyl-1-cyclohexanol　gives　an　approximate　linear　two–dimensional　aurophilic　chain,　through　intra/intermolecular　Au(I)⋯Au(I)　interactions　as　well　as　hydrogen　bonding　interactions　between　hydroxy　groups　of　alkynyl　ligands　and　PTA.　Solid　complexes　1–8　display　strongly　room/low–temperature　emissive　of　477–613　nm　with　the　emission　lifetime　of　0.40–14.0　μs.　All　the　complexes　display　higher　cytotoxicities　against　MCF-7,　with　the　cytotoxicity　decreasing　in　the　following　order　4＞8＞5＞3＞7＞6＞2＞1.　Complex　4　and　5　stand　out　for　the　highest　selectivity　towards　MCF–7　(IC50=0.63–0.78　μM)　compared　with　normal　human　embryonic　lung　fibroblasts　(helf)　(IC50=14.85–18.13　μM),　which　makes　those　complexes　attractive　for　breast　cancer　therapy.　©　2024　Wiley-VCH　GmbH.