A novel surfactant-encapsulated Sm-containing polyoxometalate was synthesized. This hybrid polyoxometalate (DDTA) 9 SmW 10 O 36 ·xH 2 O contains a hydrophobic dodecyltrimethyl ammonium shell and an encapsulated hydrophilic polyoxometalate core. (DDTA) 9 SmW 10 O 36 ·xH 2 O was synthesized by extraction procedure using chloroform as the solvent and characterized by FT–IR, UV/Vis, 1 H-NMR, and XPS. (DDTA) 9 SmW 10 O 36 ·xH 2 O readily dissolves in organic solvents such as chloroform and ethanol, from which indicates that Sm-POM has been successfully encapsulated by dodecyltrimethylammonium cations. The hybrid compound shows photoluminescence activity in the orange region of the visible light.