We report results of experimental studies on the silver clusters formation in laser desorption and matrix assisted laser desorption. Time-of-flight mass spectrometer was used to control process itself. Firstly, we investigated dependence of silver salts of variety chemical nature on formation of silver clusters. The most prominent was usage of organic silver salts (silver trifluoroacetate and silver benzoate). The biggest species obtained was Ag + 45(silver benzoate). Secondly, we examined influence of organic matrix (2,5-dihydroxybenzoic acid) on formation efficiency of silver clusters in matrix assisted laser desorption. In all cases we observed increase of silver clusters size.