In this paper, the formation, chemistry, morphology, and corrosion protection of a new type of inorganic conversion coating is described. This coating, referred to as a vanadate conversion coating (VCC), forms on aluminum alloy substrates in a matter of minutes during simple immersion in aqueous vanadate-based solutions at ambient temperatures. VCCs are yellow in color and conformal across the surface of aluminum alloy 2024-T3 (AA2024-T3 [UNS A92024]) substrates. Auger electron sputter depth profiles and x-ray absorption near-edge spectroscopy show that VCCs formed by a 3-min immersion are 300 nm to 500 nm thick and consist of a mixture of vanadium oxides and other components in the coating bath. In anodic polarization experiments conducted in aerated chloride solutions, VCCs increase the pitting potential and decrease the rate of oxygen reduction. When characterized by electrochemical impedance spectroscopy, VCCs demonstrate a low-frequency impedance between 1 MΩ-cm2 and 2 MΩ-cm2 after 24 h exposure to aerated 0.5 M sodium chloride (NaCl) solutions. In salt spray testing conducted according to ASTM B117, VCCs suppress formation of large pits for more than 168 h. VCCs also appear to be self-healing. Analysis of solution in contact with VCCs by inductively coupled plasma emission spectroscopy indicates that vanadate is released into solution upon exposure. Vanadium deposits were identified by x-ray microchemical analysis on a bare alloy substrate held in close proximity to a vanadate conversion-coated surface, and corrosion resistance of this bare surface was observed to increase during exposure. An important component of VCC formation appears to involve inorganic polymerization of V5+, which leads to the buildup of a film that passivates the surface and inhibits corrosion.