The invention relates to the technical field of coating materials and particularly relates to a solvent-free moisture-curing and electrostatic spraying white UV coating material as well as a preparation method and application thereof. The solvent-free moisture-curing and electrostatic spraying white UV coating material comprises UV resin, UV moisture-curing resin, a reactive diluent, a defoaming agent, a flatting agent, a photoinitiator, a dispersing agent, an inorganic filler, titanium dioxide, a rheological agent and a conductive agent. The solvent-free moisture-curing and electrostatic spraying white UV coating material has the characteristics of being free of VOC emission, environment-friendly, efficient, energy-saving, good in adhesive force and good in anti-sagging property; by adopting a dual curing system of combining UV curing and moisture curing, the problems that UV white electrostatic spraying is poor in anti-sagging property, poor in adhesive force and low in covering power are solved; the requirements of consumers on energy conservation, environment protection and high efficiency can be met to a greater extent; and the solvent-free moisture-curing and electrostatic spraying white UV coating material has significant market value.