Two novel hybrid Sm-containing polyoxometalates were synthesized and characterized to show that hydrophilic polyoxometalate cores are encapsulated by hydrophobic shells. Sodium salt of SmW10O369- was changed the counter ions by dodecyltrimethylammonium bromide (DDTABr) and dimethyldioctadecylammonium bromide (DODABr) to obtain (DDTA)(9)SmW10O36 and (DODA)(9)SmW10O36 . Both of them were synthesized by extraction procedure using chloroform as the solvent and characterized by FT-IR, UV/Vis, H-1-NMR, and XPS. (DDTA)(9)SmW10O36 readily dissolves in chloroform and ethanol while (DODA)(9)SmW10O36 dissolves in chloroform, toluene and benzene. The hybrid compounds show photoluminescence activity in the orange region of the visible light.