The invention discloses solvent-less ultrafine fiber high-light finish polyurethane synthetic leather. The solvent-less ultrafine fiber high-light finish polyurethane synthetic leather is composed of a surface polyurethane layer, a middle polyurethane layer, a polyether type solvent-less polyurethane layer and ultrafine fiber polyurethane synthetic leather sequentially from top to bottom. The solvent-less ultrafine fiber high-light finish polyurethane synthetic leather is prepared by the following steps: coating a high-light mirror mask with surface layer polyurethane slurry, coating middle layer polyurethane slurry after baking, coating polyether type solvent-less polyurethane slurry after baking, laminating with constant-breadth ultrafine fiber polyurethane synthetic leather after pre-reaction, conducting aging, rolling together and aging again, and stripping the high-light mirror mask to obtain the finished product. The solvent-less ultrafine fiber high-light finish polyurethane synthetic leather prepared by the invention has the following superior properties: high gloss, high flatness, no crease, smooth tactility, cuts comparable to genuine leather, hydrolysis resistance, wear resistance, normal-temperature deflection resistance, freezing resistance, high efficiency, environmental protection and the like, and can be widely applied to high grade shoes, bags, suitcases and decorative materials.