Alternating monolayers of tetrathiafulvalene and polyoxometalate clusters (see Figure) are assembled here to form hybrid Langmuir-Blodgett (LB) films. The synthetic strategy used is promising for creating multilayer structures comprising two different types of functional units that can impart an interesting combination of properties to the LB film. In the reported example, the high magnetic moment of the polyoxometalate is combined with the ability of the tetrathiafulvalene to delocalize electrons.