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This work aimed to test the efficacy of an ultrasound (US) and pulsed electric field (PEF) apparatus to extract mitragynine from dried <i>Mitragyna speciosa</i> cv. Karn Dang leaves. Four modes of the device were tested: PEF, US, US + PEF, and PEF + US, and the modes were compared using a conventional technique (maceration, as the control). The liquid chromatography/mass spectrometry (LC-MS/MS) analysis revealed that the mitragynine contents from <i>M. speciosa</i> leaves using the four different modes were significantly different (<i>p</i> < 0.05). The highest extraction (106.63 ± 0.85 mg/L) of mitragynine was obtained by the mode using a combination of PEF + US, followed by US + PEF (97.27 ± 1.33 mg/L), with increased extraction efficiencies of 45.81 ± 0.59% and 33.00 ± 1.85%, respectively. Moreover, the total energy consumption under the combination technique was 25.0% lower than that with PEF assistance. Scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR) were used to analyze the structural and functional features of the alterations in <i>M. speciosa</i> leaves. This study demonstrated that a combination of PEF and US devices may be regarded as a green alternative technique and can assist in streamlining the implementation of agricultural products.