Rare earth ion doped materials are means to obtain cost-effective infrared light sources, with enough brilliance for applications such as gas sensing. Within a sulfide matrix, the simultaneous luminescence of both Pr3+ and Dy3+ in the Ga5Ge20Sb10S65 glass is reported. The use of these two rare earths is giving rise to a broad continuous luminescence in the 2.2–5.5 µm wavelength range, which could be used as a mid-infrared light source for gas-sensing applications. The demonstration of CO2 and CH4 detection using a fiber drawn from these materials is reported.