Clinical dosimetry requires an understanding of radiation energy to accurately determine the delivered dose. For many situations this is known, however there are also many situations where the radiation energy is not well known, thus limiting dosimetric accuracy. This is the case in personnel dosimetry where thermo luminescent (TL) dosimetry is the method of choice. Traditionally beam energy characteristics in personnel dosimetry are determined through discrimination with the use of various filters fitted within a radiation monitor. The presence of scattered and characteristic radiation produced by these metallic filters, however, can compromise the results. In this study the TL response of five materials TLD100, TLD100H, TLD200, TLD400 and TLD500, was measured at various X-ray energies. The TL sensitivity ratio for various combinations of materials as a function of X-ray energy was calculated. The results indicate that in personal dosimetry a combination of three or more TL detector system has a better accuracy of estimation of effective radiation energy of an X-ray beam than some of the current method of employed for energy estimation and has the potential to improve the accuracy in dose determination in a variety of practical situations. The development of this method also has application in other fields including quality assurance of the orthovoltage therapy machines, dosimetry intercomparisons of kilovoltage X-ray beams, and measurement of the dose to critical organs outside a treatment field of a megavoltage therapy beam.