We present three new spectra of the nearby Type Ia supernova (SN Ia) 2011fe covering ≈ 480 − 850 days after maximum light and show that the ejecta undergoes a rapid ionization shift at ∼ 500 days after explosion. The prominent [Fe III] emission lines at ≈ 4600 Å are replaced with the permitted Fe I+Fe II blends at ∼ 4400 Å and ∼ 5400 Å. The ≈ 7300 Å feature, which is produced by [Fe II] +[Ni II] at 400 days after explosion, is replaced by broad (≈ ±15 000 km s −1 ) symmetric [Ca II] emission. The change in emission characteristics is likely due to the temperature in the inner ejecta dropping below the level needed to populate the high-ionization Fe III transitions. This ionization shift corresponds to a distinct temperature and density in the ejecta and may be useful as a probe of the ejecta's temporal evolution. Models predict this ionization transition occurring ∼ 100 days later than what is observed which we attribute to clumping in the ejecta. Finally, we discuss the reliability of [Ca II] as an ejecta diagnostic feature.