Cross sections for ionization excitation of molecules by positron impact have been measured for the first time by scattering a positron beam from CO2 and N2. The cross sections have been observed to exceed those for electron impact by up to a factor of approximately 3 for CO2 and approximately 5 for N2. The enhancement arises primarily via positronium formation. The cross sections account for up to approximately 12% and 20% of the total cross sections for positron scattering from N2 and CO2, respectively.