The thickness of each layer in a multilayered system is determined by a Fourier-transform method using spectroscopic reflectance measurements. To verify this method, we first generate theoretical reflectance spectra for three layers, and these are fastFourier-transformed using our own Matlab program. Each peak of the Fourier-transformed delta function denotes the optical thickness of each layer, and these are transformed to physical thicknesses. The relative thickness error of the theoretical model is less than 1.0% while a layer's optical thickness is greater than 730 nm. A PI-(thin SiO2)-PImultilayeredstructure produced by the bar-coating method was analyzed, and the thickness errors compared to SEM measurements. Even though this Fourier-transform method requires knowing the film order and the refractive index of each layer prior to analysis, it is a fast and nondestructive method for the analysis of multilayered structures.