Effective atomic numbers for total gamma-ray interaction with some selected thermoluminescent dosimetric compounds such as barium acetate, barium sulfate, calcium carbonate, calcium sulfate, calcium sulfate dihydrate, cadmium sulfate (anhydrous), cadmium sulfate, strontium sulfate, and lithium fluoride have been calculated in the 1-keV to 20-MeV energy region. Experimental mass attenuation coefficients and effective atomic numbers for these compounds at selected photon energies of 26.3, 33.2, 59.54, and 661.6 keV have been obtained from good geometry transmission measurements and compared with theoretical values. The effect of absorption edge on effective atomic numbers and its variation with energy, and nonvalidity of the Bragg's mixture rule at incident photon energies closer to the absorption edges of constituent elements of compounds are discussed.