An X-ray fluorescence spectrometer includes an X-ray source 7 for irradiating a sample 1 at a predetermined incident angle ø with primary X-rays 6, and a detecting device 9 for measuring an intensity of fluorescent X-rays 8 generated from the sample at a predetermined detection angle α and β, wherein with two combinations of the incident angle ø and the detection angle α and β, in which combinations the incident angles ø and/or the detection angles α and β are different from each other, each intensity of the fluorescent X-rays 8 is measured and, also, the incident angle ø and the detection angle α and β in each of the combination are so set that with respect to a measurement depth represented by the coating weight, at which the intensity of the fluorescent X-rays 8 attains a value equal to 99% of the uppermost limit when the coating weight of a target coating to be measured is increased, respective measurement depths in the two combinations may be a value greater than the coating weight of a coating 3.