Abstract In the diagnosis of vacuum discharge plasma using the Langmuir probe, the electron energy distribution function(EEDF) is closely related to the second derivative of current to voltage (d2I/dV2) on the Langmuir probe. While d2I/dV2 is very sensitive to probe noise, its accuracy directly affects the measurement results of the electron energy distribution function. In this paper, a modified AC modulation method is proposed to improve the measurement accuracy of the electron energy distribution function. First, two small AC signals of different amplitudes are modulated on the measured DC scanning voltage of the Langmuir probe, and the probe current signal is measured. Then, the fundamental amplitudes of the two AC signals are corrected by spectral analysis and using the all-phase Fast Fourier Transformation - Fast Fourier Transformation(apFFT-FFT) amplitude correction algorithm. Then the accurate first-order derivative of the probe current to voltage (dI/dV) is obtained using the AC modulation derivative correction algorithm, and finally the electron energy distribution function is obtained by numerically differentiating dI/dV to obtain d2I/dV2. The method of this paper is compared with the traditional data processing method through experiments, and the results show the superiority and effectiveness of the method.