Three different Gemini compounds containing different lengths of multi-carbonyl groups were synthesized, and the effect of their hydrocarbon tail length on the AgNPs synthesis was investigated. The Gemini surfactants with the long hydrocarbon chain tail produces small AgNPs with a narrow size distribution and high colloidal stability in an aqueous phase. The surface parameters of the aqueous solution were affected by the hydrocarbon chain length as well as phase temperature. The critical micelle concentration, assessed by surface tension and conductometric measurements, decreases with both increasing solution temperature and increasing hydrocarbon tail length. Thermodynamic calculations predicted the ability of the synthesized Gemini surfactant to adsorb on the phase surface and aggregate in a cluster.