We make a new type of bipolar Schottky diodes using the p-type La2/3Sr1/3VO3 (LSVO)/n-TiO2 heterostructure. The p-type LSVO metal thin films are grown on various substrates using radio frequency magnetron co-sputtering deposition. We find that the LSVO film grown on anatase TiO2 layer produce the lowest resistivity of 0.28 m Omega cm. We discover that the resistivity decreases with decreasing LSVO film thickness for LSVO/TiO2/Si structures. Hall measurements are performed and the dielectric functions of LSVO films are measured. The effective mass of LSVO/TiO2/Si is determined to be 2.54 +/- 0.05 m(0). The current-voltage curves of the Schottky diodes of p-LSVO/n-TiO2 is measured and is explained using band alignment diagram. We identify a new type of Schottky diode, where both electrons in n-TiO2 and holes in p-LSVO can flow under bias.