Zinc forms a variety of structures with vanadium oxide. We review and report here on four compounds formed by mild hydrothermal synthesis in the presence of the tetramethyl ammonium ion, which tends to stabilize layered vanadium oxide structures. These invariably contain protons either in the form of hydroxyl ions or as structural water. The compounds include Zn 3 (OH) 2 (V 2 O 7 )*2H 2 O, which contains V 2 O 7 pillars, Zn 2 (OH) 3 (VO 3 ), and the two related double sheet vanadium oxides δ-Zn 0 . 8 V 4 O 1 0 *0.6H 2 O and [N(CH 3 ) 4 ] 4 [Zn 4 V 2 1 O 5 8 ]. We report the new structure of the last, which was determined from micron size crystals, and compare it to other double sheet structures. These compounds provide model systems to study ionic mobility and reversible redox chemistry.