It is well known that x-ray photoelectron spectroscopy (XPS) is a meaningful analytical technique for the chemical characterization of material surface, but the detection limit of XPS is inferior to that of other methods, such as secondary ion mass spectrometry (SIMS) and total reflection x-ray fluorescence (TXRF) analysis. Recently, in developing a new DRAM, the energy of P and B injected into an Si wafer was bound to be lowered. Accordingly, the investigation of the chemical bonding states of these elements on the Si wafer surface has become important. Since B1s and P2p photoelectron peaks overlap with the energy loss peaks of Si2s and Si2p peaks, it is difficult to detect a small amount of B and P injected into the Si wafer by XPS. Therefore, the use of x-ray total reflection has become noteworthy in photoelectron spectroscopy. This is because TRXPS (total reflection x-ray photoelectron spectroscopy) can greatly reduce the number of inelastically scattered electrons contributing to the background of photoelectron spectrum, as the effective analysis depth of TRXPS is nearly equal to the x-ray penetration length in the solid. In addition to this, TRXPS is expected to give a lower detection limit. In this work, we examined the chemical bonding state of B and P on the Si wafer by means of TRXPS. In what follows, the effectiveness TRXPS method to the semiconductor surface analysis will be described.