The angular dependence of the x-ray fluorescence from Y and Mn inner K shell ionization induced by a grazing angle incident electron beam in several multilayered Y/Mn structures was analyzed using the distorted-wave approximation. Estimates of structural parameters, thickness, and interfacial roughness were obtained from the x-ray fluorescence measured in the total reflection regime and compared with ex situ x-ray reflectivity results. Although the sensitivity to the surface and interface roughness was relatively low, the thickness values for both single and buried layers were in good agreement with the x-ray reflectivity measurements.