To provide a method and an apparatus, for a total reflection X-ray fluorescence analysis, in which a part near the side end face of a sample can be analyzed and in which the sample can be used effectively.

In this total reflection X-ray fluorescence analysis, a visual-field limitation member 6 which comprises a plurality of slits is arranged between a sample 50 and an X-ray detector 4 so as to be capable of being changed over. When a part near the side end face of the sample is analyzed, the limitation member is changed over to a second slit 62 whose opening area is smaller than that of a first slit 61 used for an ordinary analysis. A visual field is limited in such a way that fluorescent X-rays and scattered X-rays from the side end face of the sample are not taken into the X-ray detector 4. Consequently, even when the part near the side end face of the sample is analyzed, the fluorescent X-rays and the scattered X-rays from the side end face of the sample are not taken into the X-ray detector 4, and the sample 50 including the part near the side end face can be analyzed as a whole. A specific place which is narrower than the sample can be analyzed by the second slit 62.