We report the use of two Raman signatures, the Bi-induced longitudinal-optical-plasmon-coupled (LOPC) mode and the GaAs Fröhlich scattering intensity, present in nominally undoped (100) GaAs1−yBiy to predict the 300K photoluminescence intensity and Bi composition (y) in GaAs1−yBiy. The LOPC mode is used to calculate the hole concentration in GaAs1−yBiy epitaxial layers. A linear relationship between hole concentration and photoluminescence intensity is found for a range of samples grown at various temperatures and growth rates. In addition, the composition (y) of Bi in GaAs1−yBiy is also found to be linearly related to the GaAs Fröhlich scattering intensity.