The invention relates to an STED (stimulated emission depletion)-based device and method for measuring a smooth free-form surface sample, belonging to the field of the optical microscopic measurement. The device comprises a first picosecond pulse laser, a first conduction optical fiber, a first collimator objective, a first plane reflecting mirror, a second picosecond pulse laser, a second conduction optical fiber, a second collimator objective, a second plane reflecting mirror, a vortex-shaped phase modulation plate, a half-wave plate, a first dichroscope, a second dichroscope, a quarter-wave plate, a focusing object lens, a coating sample, a three-dimensional micro-displacement carrier table, an optical filter, a collection object lens, a pin hole and a photoelectric detector. The surface of the sample is coated with a fluorescent membrane, so that an industrial sample can be measured by utilizing the STED microscopy; meanwhile, the fluorescent membrane radiates fluorescence in different directions under the illumination of the laser, so that the problem that the signal light is difficult to collect caused by the mirror reflection of the light beam on a smooth free-form surface can be avoided. By adopting the device and method, the surface appearance of the smooth sample with a large angle between a normal and the optical axis direction can be high precisely measured.