The polyvalent cations Mg2+, Zn2+, and Al3+ were intercalated into V2O5 aerogel to a maximum concentration of 4, 2.5, and 3.33 equiv, respectively, per mole of V2O5. The intercalation was reversible in each case, analogous to the intercalation of Li+ ions. Pillaring of the host facilitates the intercalation process.