The efficiency of single-junction solar cells is limited to about 30% (the Shockley-Queisser limit). Spectral mismatch losses (transparency to low-energy photons, thermalization of high-energy photons) strongly contribute to lowering the maximum efficiency. To reduce thermalization losses, photon splitting is proposed and observed for a variety of lanthanide-doped materials. For , even a one-to-three photon-splitting process has been reported, yielding three IR photons at around 1530 nm following absorption of one blue-green photon. This is especially beneficial for narrow band gap solar cells, such as crystalline . Here, we report on photon splitting for in . Following absorption in the and levels (520–550 nm), efficient cross-relaxation (CR) yields two excited ions: one in the state and one in the state (CR1). A second CR step from the state, leaving both ions in the excited state (CR2), is crucial in realizing efficient three IR photon splitting. It is demonstrated here that the second step has a low efficiency, as a result of competing fast multiphonon relaxation, , and a large energy mismatch, which makes the CR2 step thermally activated. Based on experiments and theory, a maximum quantum efficiency of 170% is calculated for IR emission, following blue-green excitation in . An outlook is presented for three-photon splitting in low-phonon-energy hosts, where nonradiative multiphonon relaxation is suppressed. The anti-Stokes nature of the second CR step makes three-photon splitting unlikely and prevents the realization of IR quantum yields above 200%.