GaNyAs1-x-yBix alloys were grown by molecular-beam epitaxy using solid Ga, Bi, and As sources and nitrogen radicals generated from nitrogen gas in rf plasma. Changing the growth temperature is found to be a convenient method for controlling the GaBi molar fraction in the alloy reproducibly. The photoluminescence (PL) spectra show that the PL peak energy of GaNyAs1-x-yBix alloy decreased with increasing GaBi and GaN molar fractions. The redshift coefficients of ∼62 meV/%Bi and ∼130 meV/%N at the PL peak energy of GaNyAs1-x-yBix were observed at room temperature. The temperature dependence of the PL peak energy in the temperature range of 150–300 K is much smaller than the temperature dependence of the band gap of InGaAsP. The temperature coefficients of GaAs1-xBix and GaNyAs1-x-yBix band gaps are governed by the GaBi molar fraction and they decrease with increasing GaBi molar fraction. GaNyAs1-x-yBix alloys with different PL peak energies and lattice matched to GaAs substrates were obtained. The photoluminescence peak energy was located at a predicted wavelength for the sample lattice matched to GaAs which was found to have the structure of - Ga(N0.33Bi0.67)zAs1-z.