In this work, the structural and electrical properties of amorphous and crystalline Ta2O5 thin films deposited on p-type Si substrates by low-pressure chemical vapor deposition from a Ta(OC2H5)5 precursor have been investigated. The as-deposited layers are amorphous, whereas crystalline Ta2O5 was obtained after postdeposition O2 treatment at 800 °C. As evidenced by x-ray diffraction, a hexagonal structure was obtained in the latter case. Physicochemical analysis of our layers shows that the O2-annealing step leads to the growth of a thin (∼1 nm) interfacial SiO2 layer but was not sufficient to reduce the level of hydrocarbon contamination. The dominant conduction mechanism in amorphous Ta2O5 is clearly due to the Poole–Frenkel effect, whereas the situation remains unclear for crystalline Ta2O5 for which no simple law can be invoked to correctly describe its conduction properties. From capacitance–voltage measurements, the dielectric constant was found to be ∼25 for amorphous samples, but values ranging from 56–59 were found for crystalline layers, suggesting a particularly high anisotropic character of the crystalline phas- e. Finally, the effects of postdeposition annealing in N2 and forming gas at 425 °C have been investigated for both types of films. © 1998 American Institute of Physics.