On 15 July 2004, the Ozone Monitoring Instrument (OMI) on board the EOS Aura mission was launched. One of OMI's priorities is to continue the record of high spatial resolution ozone total column measurements provided by the various Total Ozone Mapping Spectrometer (TOMS) instruments since 1978. To this end, it is essential to estimate the errors affecting OMI ozone total column measurements and to see whether the actual accuracy is consistent with estimated values before launch. In this paper, data assimilation techniques are used to create a large comparison data set composed of ozone analyses resulting from assimilation of standard meteorological observations and ozone retrievals (independent of OMI measurements) into a numerical weather prediction model. This data set provides excellent global coverage and temporal resolution, not limited by the spatial and temporal distribution of other satellite or ground based information. The accuracy of the analyses is evaluated against ozone total column retrievals from Brewer measurements, while the assimilated ozone data set is compared to ozone predictions made using the ECMWF model, to check for the presence of bias. The OMI ozone column measurements considered here are obtained with the TOMS-V8 total ozone algorithm and denoted as OMTO3 columns. They are compared with simulated OMI ozone columns, i.e., the quantities that the TOMS-V8 algorithm would retrieve in the case when the atmospheric ozone profile at a specific location and time is equal to the one prescribed by the analysis. In this way, the comparison is statistically robust even when data acquired during a relatively short temporal interval or over a relatively small geographical area only is considered. A discussion of relevant error sources (including systematic components), vertical resolution, and contributions from prior information is provided. Special attention is given to determining the importance of representativeness errors. Our results show a solar zenith angle (SZA) dependence of the bias between measured and simulated OMI columns. This is believed to be due to moderate nonlinearity of the observation forward model and its effects on our definition of simulated OMI columns at high SZA. In view of these findings the final results of the intercomparison methodology used in this paper are obtained from OMI ozone columns retrieved using the basic implementation of the TOMS-V8 algorithm applied to measurements taken at SZA not exceeding 70°. Intercomparison results between measured and simulated OMI ozone columns at SZA less than 70° show a relative bias of −3.2 ± 3.1% and a root-mean-square error of 4.5 ± 1.5%. The resulting bias is consistent with available estimates of the bias of OMTO3 columns with respect to SBUV/2 between 60°S and 60°N, as well as with respect to global Dobson data and Brewer measurements between 30°N and 60°N.