Neutral macrocyclic compounds (crown ethers and cryptands) and charged molecular species (alkylammonium iodides) were intercalated into vanadium oxide xerogel (V2O5 · nH2O) to study their influence on the electrical behaviour of this inorganic 2D host lattice. Treatment with alkyl or arylammonium iodide solutions produced the intercalation of organic cations accompanied by the reduction of a fraction of V (V) to V (IV). Characterisation by different techniques allowed the postulation of the interlayer arrangement of the guest species. The study of electrical behaviour at different temperatures indicated that the properties of the hybrid materials can be mainly related to the nature of guest species, the degree of host lattice reduction, the interlayer water content, and the presence of metal ions deliberately introduced in the system.