Recent work has shown that there is significant uncertainty in measuring build-up doses in mega-voltage photon beams especially at high energies. In this present investigation we used a phantom-embedded extrapolation chamber (PEEC) made of Solid Water to validate Monte Carlo (MC)-calculated doses in the dose build-up region for 6 and 18 MV x-ray beams. The study showed that the percentage depth ionizations (PDIs) obtained from measurements are higher than the percentage depth doses (PDDs) obtained with Monte Carlo techniques. To validate the MC-calculated PDDs, the design of the PEEC was incorporated into the simulations. While the MC-calculated and measured PDIs in the dose build-up region agree with one another for the 6 MV beam, a non-negligible difference is observed for the 18 MV x-ray beam. A number of experiments and theoretical studies of various possible effects that could be the source of this discrepancy were performed. The contribution of contaminating neutrons and protons to the build-up dose region in the 18 MV x-ray beam is negligible. Moreover, the MC calculations using the XCOM photon cross-section database and the NIST bremsstrahlung differential cross section do not explain the discrepancy between the MC calculations and measurement in the dose build-up region for the 18 MV. A simple incorporation of triplet production events into the MC dose calculation increases the calculated doses in the build-up region but does not fully account for the discrepancy between measurement and calculations for the 18 MV x-ray beam.