The invention discloses a coaxial jet head for electro-hydrodynamic jet printing, which comprises a probe-placed platform, a nozzle, a support seat, a metal probe and a lip sleeve, wherein the nozzle is fixedly arranged on the probe-placed platform, the support seat is arranged at the upper end of the nozzle, the lip sleeve is sleeved on a spout at the lower end of the nozzle, an probe sleeve at the upper end of the metal probe is sleeved in a central screwed hole of the support seat, a probe body is arranged in an inner cavity of the nozzle, the axis line of the probe body and the central axis line of the nozzle are coaxial, and a probe tip at the lower part of the metal probe passes through a through hole in the lip sleeve and stretches out the nozzle. The invention also discloses the application of the jet head in preparing micro-nano fiber. By using the coaxial jet head disclosed by the invention, the control precision of ink supply amount can be increased; and through replacing the lip sleeve, a serialized jet head can be formed, thereby solving the problem that small-inside-diameter nozzles are blocked easily and solutions in large-inside-diameter nozzles easily naturally drop, solving the problem that a solid metal probe can not be continuously supplied with ink, and effectively reducing the critical voltage value of process-required exerted external voltage.