We reported the growth and its electrical properties of [100]-oriented diamond film using alcohol and hydrogen by HFCVD. SEM and Raman measurements indicated that high quality polycrystalline diamond films with [100]-faced structure were obtained. Dark current–voltage (I–V), capacitance–frequency (C–F), capacitance–voltage (C–V) and photocurrent under steady-state 55Fe 5.9keV X-ray excitation of freestanding diamond film were investigated at room temperature. Results indicated that after post-annealing for [100]-oriented diamond films dark current was in the order of 10−10A and the photocurrent was of in the order 10−8A by X-ray irradiation with the applied voltage of 40V, capacitance and dielectric loss were very small with the value of 2pF and 2×10−3 with the bias voltage of 0.05V, respectively, and almost had no variation with the change of frequency in high frequencies from 100kHz to 10MHz.