A variety of functional nanostructured organic/inorganic hybrid materials from the europium-exchanged derivative of a Preyssler-type polyoxometalate (POM), [EuP5W30O110]12−, and functional organic surfactants were prepared by the ionic self-assembly (ISA) route. The effect of organic surfactants on the structure, photoluminescent, electrochemical and electrochromic properties of the POM anions was investigated in detail. All obtained hybrid materials are amphotropic, i.e., exhibit both thermotropic and lyotropic liquid-crystalline phase behaviour. Investigations of their photophysical properties have shown that the interactions of the various surfactants with the polyanions influence the coordination environments and site symmetry of Eu3+ in different ways. The functional groups in the organic surfactants significantly influence the electrochromic properties and photoluminescence of POMs. Different from normal and pyridine-containing complexes, no photoluminescence and no electrochromism were observed from the ferrocene-containing complexes. This may be explained in view of charge transfer between the POM anion and the ferrocenyl group.