Mean mass energy absorption coefficient ratios of acrylic, polystyrene, and water to air, were calculated using Monte Carlo generated energy spectra. The energy spectra were calculated for 4‐ to 50‐MV x‐ray beams, from machines using flattening filters and scanning beams. The validity of these spectra was verified by comparing the measured ionization ratios with the calculated values. The agreement was found to be within 1.9%. For beams of energy below 6 MV, our estimates of the mean mass energy absorption coefficient ratios agree well with those recommended by the TG‐21 protocol. For higher energy beams, the discrepancy increases to about 3%. It was found that the discrepancy is attributable to the different spectra used in these calculations.