Total photon atomic cross sections in elements Zr, Ag, Ta and Th were determined around theirK-edges in the energy region 6 to 400 keV with a good geometry set-up using proportional counter or Ge(Li) detector system. From these values the photoelectric cross sections were obtained by subtracting the theoretical values of coherent and incoherent scattering cross sections. The resulting photoelectric cross sections were fitted to curves above and below theK-edge for each element and extrapolated on either side and the total toK-shell photoelectric cross section ratios were determined with an error not exceeding 2%. The ratios were compared with the theoretical values obtained by Grodstein and others, as also from the empirical relation of Hubbell. The present values show good agreement with those of Scofield. A definite trend of decrease of the ratio as the energy increases is observed in the case of Th unlike in the previous experimental studies.