In summary, high signal intensities of fragment ions, which are not typically observed in full scan MS with soft ambient ionization methods, were detected in our investigation. A key observation is that MPTDI-TOF MS is able to produce higher abundances of MSn fragmentation ions when microwave power is set to >60 watt. The information of protonated molecular ions, molecular ions, and fragment ions could be obtained in the full-scan mass spectra of MPTDI-TOF under the conditions of 30 s of desorption time, 5 mm of desorption distance, and 70 watt of microwave power.