A traditional double monochromatic measurement instrument of diffraction efficiency for a plane grating involves two major problems: one is the differences of output spectrum bandwidths during measurement of a standard reflection mirror and the tested grating; the other is overlapping of diffracted spectra, which influence testing accuracy of diffraction efficiency. In this paper, a new measuring method of diffraction efficiency based on Fourier spectral technology is presented. The mathematical model of diffraction efficiency is first deduced and then verified by ray tracing and Fourier optics simulation. The influences of the moving cube corner's tilt error, lateral shift error, and maximal moving distance error on the measurement accuracy are analyzed in detail. The analyses provide theoretical references for designing diffraction efficiency instruments. Compared with the traditional diffraction efficiency measurement instrument with double monochromator structure, our method not only improves the measurement accuracy of diffraction efficiency but also has the advantage of high luminous flux, high spectral resolution, multiwavelength measurement in mean time, and high wavenumber accuracy.