Small aluminum-vanadium oxide clusters, AlVOy- (y = 1-3) and AlxVO2- (x = 2, 3), were investigated with anion photoelectron spectroscopy and density functional calculations. The adiabatic detachment energies of AlVOy- were estimated to be 1.06 +/- 0.05, 1.50 +/- 0.08, and 2.83 +/-0.08 eV for y = 1, 2, and 3. Those of Al2VO2- and Al3VO2- were estimated to be 1.22 +/- 0.08 and 1.25 +/- 0.08 eV. Comparison of theoretical calculations with experimental measurement suggests that the most probable structure of AlVO- cluster is quasilinear with O atom in the middle. AlVO2- has an irregular chain structure of Al-O-V-O and a C-2v cyclic structure very close in energy. The structure of AlVO3-cluster is evolved from the C-2v cyclic AlVO2- structure by adding the third O atom to the V atom. Al2VO2- has a pair of nearly degenerate Al-O-V-O-Al chain structures that can be considered as cis and trans forms. Al3VO2- probably has two low-lying isomers each containing a four-membered ring. The structures of the corresponding neutral clusters are discussed.