The electrical characteristics of thin TiO2 films prepared by metal–organic chemical vapor deposition grown on a p-type InP substrate were studied. For a TiO2 film of 4.7 nm on InP without and with ammonium sulfide treatment, the leakage currents are 8.8×10−2 and 1.1×10−4 A/cm2 at +2 V bias and 1.6×10−1 and 8.3×10−4 A/cm2 at −2 V bias. The lower leakage currents of TiO2 with ammonium sulfide treatment arise from the improvement of interface quality. The dielectric constant and effective oxide charge number density are 33 and 2.5×1013 cm2, respectively. The lowest mid-gap interface state density is around 7.6×1011 cm−2 eV−1. The equivalent oxide thickness is 0.52 nm. The breakdown electric field increases with decreasing thickness in the range of 2.5 to 7.6 nm and reaches 9.3 MV/cm at 2.5 nm.