The basic solution properties of the newly synthesised hedgehog-shaped polyoxomolybdate, Na48[HxMo256VIMo112VO1032(H2O)240(SO4)48]⋅ca.1000H2O, x≈16 ({Mo 368 }, “blue nanolemon”), were investigated by conductivity curves, pH curves, influence of additive electrolytes, and surface modification by a cationic surfactant, tetradecyltrimethylammonium bromide (TTA + Br − ). For 1.25×10 −5 molL −1 {Mo 368 } aqueous solution, the average {Mo 368 } n− surface can be encapsulated by 122±5 TTA + , which allows a spatial arrangement. In addition, the larger clusters with a hydrophilic or hydrophobic surface and monolayer or bilayer capsules were subsequently formed by surface modification of TTA + . At the stoichiometric ratio, {Mo 368 } and TTA + Br − can spontaneously self-assemble to form a hydrophobic surfactant-encapsulated cluster (SEC), {Mo 368 } 122− –(TTA + ) 122 , which is a novel inorganic/organic nano-complex. From experiments, it was found that many TTA + cations arrange orderly on the surface of giant anions {Mo 368 } n− , like reversed micelles. But the complex is poorly crystalline because of the surfactant encapsulation, which makes a few gauche defects in the complex. This topic bridges the channel between inorganic chemistry and colloidal chemistry.