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This letter deals with the electroluminescence emission at room temperature of two light-emitting diodes on GaP substrate, based on ternary GaAsP/GaP and quaternary GaAsPN/GaPN multiple quantum wells. In agreement with tight-binding calculations, an indirect band gap is demonstrated from the temperature-dependent photoluminescence for the first structure. High efficiency photoluminescence is then observed for the second structure. Strong electroluminescence and photocurrent are measured from the diode structures at room temperature at wavelengths of 660 nm (GaAsP/GaP) and 730 nm (GaAsPN/GaPN). The role of the incorporation of nitrogen on the optical band gap and on the nature of interband transitions is discussed.