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A new calibration technique for PVDF ultrasonic hydrophone probes is described. Current implementation of the technique allows determination of hydrophone frequency response between 2 and 100 MHz and is based on the comparison of theoretically predicted and experimentally determined pressure-time waveforms produced by a focused, circular source. The simulation model was derived from the time domain algorithm that solves the non linear KZK (Khokhlov-Zabolotskaya-Kuznetsov) equation describing acoustic wave propagation. The calibration technique data were experimentally verified using independent calibration procedures in the frequency range from 2 to 40 MHz using a combined time delay spectrometry and reciprocity approach or calibration data provided by the National Physical Laboratory (NPL), UK. The results of verification indicated good agreement between the results obtained using KZK and the above-mentioned independent calibration techniques from 2 to 40 MHz, with the maximum discrepancy of 18% at 30 MHz. The frequency responses obtained using different hydrophone designs, including several membrane and needle probes, are presented, and it is shown that the technique developed provides a desirable tool for independent verification of primary calibration techniques such as those based on optical interferometry. Fundamental limitations of the presented calibration method are also examined.