The invention discloses a controllable high-voltage direct current power supply for an ESI source. The controllable high-voltage direct current power supply comprises an oscillating module, a switching module, a boosting module, a voltage-multiplying rectifying module, a filtering module and an output module, wherein the oscillating module is used for conducting self-oscillation and generating switching signals, the switching module is used for conducting alternate connection under the control of switching signals to output initial alternating voltage, the boosting module is used for boosting the initial alternating voltage to obtain second alternating voltage, the voltage-multiplying rectifying module is used for boosting the second alternating voltage according to a preset multiple and rectifying the boosted voltage to output direct voltage, the filtering module is used for filtering the direct voltage, and the output module is used for outputting the filtered direct voltage. The invention also discloses the ESI source. According to the controllable high-voltage direct current power supply and the ESI source, the high voltage and a strong electric field are provided for the ESI source, so that the ionizing efficiency of samples and the transmission efficiency of produced ions can be greatly improved.