This paper presents details concerning such spurious peaks as Fe Ka and Ni Ka radiation, which are often observed in the trace determination of metallic impurities on silicon wafers by using a monochromatic total reflection X-ray fluorescence (TXRF) analyzer. The intensity of a spurious peak varies along with changes in the incident azimuth angle and/or detected intensity of the primary X-ray beam. The origin of this phenomenon is impurities existing along the path of Xrays. This phenomenon influences the accuracy of trace TXRF analysis, and a practical detection limit of a TXRF analyzer becomes worse by approximately one order, becoming 10" atoms/cm2, than the calculated detection limit (2 -8X1010 atoms/cm2) in our case.