The synthesis of the first mesogenic donor‐acceptor polyoxometalate (POM)‐based hybrid is herein described. The structural and electronic properties of the hybrid compound were evaluated through combination of small‐ and wide‐angle X‐ray scattering, optical microscopy, electrochemistry and photoluminescence. In the solid state, the compound behaves as a birefringent solid, displaying a lamellar organization in which double‐layers of POMs and bis(thiophene)thienothiophene organic donors alternate regularly. Noticeably, the sub‐unit organizations in the composite are similar to that observed for the individual POM and organic donor precursors. Photophysical studies show that in the hybrid, the fluorescence of the organic donor unit is considerably quenched both in solution and in the solid state, which is attributed to occurrence of intramolecular charge‐separated state. The synthesis of the first mesogenic donor‐acceptor polyoxometalate (POM)‐based hybrid is presented. In the solid state, the compound displays a lamellar organization in which the sub‐unit organizations are similar to that observed for the individual POM and organic donor precursors. The fluorescence of the donor is considerably quenched both in solution and in the solid state, which is attributed to the occurrence of charge transfer.