Optical constants of III-V materials in a GaAsP/SiGe tandem cell are investigated. Spectroscopic ellipsometry with techniques to improve uniqueness are used. Complex indices of refraction of GaAs.84P.16, Ga.59In.41P and Al.65In.35P are found. The results are some of the first published for alloys not lattice-matched to GaAs. This has the potential to improve interpolation of constants for additional alloys.