The reaction of silver acetate with a phosphinothiosemicarbazone ligand, HLPPh, yielded the tetranuclear silver compound [Ag-4(LPPh)(4)]. 2MeOH (1), which after recrystallization results in the cocrystallization of two different silver clusters, [Ag-4(LPPh)(4)](a)-[Ag-4(LPPh)(4)](b) center dot 8MOH (2). The factors involved in the assembly of tetranuclear compounds derived from thiosemicarbazone ligands and the structural differences between the two clusters are analyzed herein. Additionally, HLPPh and complex 1 exhibit photoluminescence in solution at room temperature.