Accurate photoionization rates are vital for the study and understanding of ionospheres and may account for the discrepancy in electron densities and mismatched altitude profiles of current E-region models. The underestimation of electron density profiles could be mitigated by high-resolution cross sections that preserve autoionization lines which allow solar photons to leak through to lower altitudes. We present new ionization rates calculated with high-resolution (0.001 nm) O and N2 photoionization and electron impact cross sections, and a high-resolution solar spectrum as inputs to CPI’s Atmospheric Ultraviolet Radiance Integrated Code [AURIC, Strickland et al., 1999]. The new electron impact cross sections show little structure and have minimal effect on calculations of ionization rates. Results from AURIC with updated O and N2 cross sections indicate increased production rates up to ~40% in the E-region, specifically between 100–115 km. Likewise, production rates determined using the ionospheric photoionization rate code from Meier et al. [2007] also illustrate an increase in the O and N2 production rates (typically of more than 10%) when using the newly calculated cross sections. Additionally, we find that O and N2 dominate the volume production rates above 130 km while O2 is expected to be the main contributor from 95–130 km. AURIC model results that use the default data and model results with the new O and N2 cross sections both track very well with electron density profiles determined from Arecibo ISR observations. AURIC model results using the new cross section calculations are in better agreement with Arecibo observations at higher altitudes. Our current findings indicate that O2 plays a dominant role in photoionization production rates in the E-region. Therefore it is crucial to update ab initio ionospheric models with high-resolution photoionization cross sections.