Variation of the reaction conditions with AgC CR (R = Ph, C6H4OCH3-4, Bu-t), (BuPO3H2)-Bu-t, and AgX (X = NO3, BF4) as starting materials afforded four new silver(I) ethynide complexes incorporating the tert-but ylphosphonate ligand, namely, 3AgC CPh center dot(Ag2BuPO3)-Bu-t center dot(AgBuPO3H)-Bu-t center dot 2AgNO(3) (1), 2AgC CC6H4OCH3-4 center dot(Ag2BuPO3)-Bu-t center dot 2AgNO(3) (2), [{Ag-5(NO3@Ag-18)Ag-5}((BuC)-Bu-t C)(16)((BuPO3)-Bu-t)(4)(H2O)(3)][{Ag-5(NO3@Ag-18)Ag-5} ((BuC)-Bu-t C)(16)((BuPO3)-Bu-t)(4)(H2O)(4)]center dot 3SiF(6)center dot 4.5H(2)O center dot 3.5MeOH (3), and [{Ag-8(Cl@Ag-14)}((BuC)-Bu-t C)(14)((BuPO3)-Bu-t)(2)F-2(H2O)(2)]BF4 center dot 3.5H(2)O (4). Single-crystal X-ray analysis revealed that complexes 1 and 2 display different layer-type coordination networks, while 3 and 4 contain high-nuclearity silver(I) composite clusters enclosing nitrate and chloride template ions, respectively, that are supported by (BuPO32-)-Bu-t ligands.