A cycling electrospray ionization device includes a driving mechanism and a nozzle. The nozzle is configured to sequentially form liquid droplets of an electrospray medium thereat, and is adapted to establish a traveling path with a receiving unit of a mass spectrometer such that when a potential difference is applied between the nozzle and the receiving unit to lade the liquid droplets with a plurality of electric charges for ionizing analytes to form ionized analytes, the charged droplets are forced to move toward the receiving unit along the traveling path. The nozzle defines a nozzle axis, and is driven by the driving mechanism to proceed with a cycling route about a cycling axis such that the nozzle axis tracks along the cycling route, and such that immediately after leaving the nozzle, the liquid droplets cooperate to form a substantially columnar plume with a cross section substantially surrounded by the cycling route.