The X-ray fluorescence spectrometer of the present invention includes a sample table (8) for a sample (S) having a crystalline structure, an X-ray source (1), a detecting unit (7) for detecting secondary X-rays (4) from the sample (S), a rotating unit (11) for rotating the sample table (8), a parallel translating unit (12) for causing the sample table (8) to undergo a parallel translational movement, a selecting unit (17) for selecting three of circumvent angles, at which diffracted X-rays can be circumvented, based on a diffraction profile obtained from the angle of rotation of the sample (S) and the intensity of secondary X-rays (4), the interval between the neighboring circumvent angles being smaller than 180°, and a control unit (15) for controlling the rotating unit (11) so as to set the sample (S) at the circumvent angle at which the sample table (8) will not interfere with any other structures.