This Letter theoretically discusses the photon emission spectra of a superconducting p-n junction. On the basis of the second order perturbation theory for electron-photon interaction, we show that the recombination of a Cooper pair with two p-type carriers causes enhancement of the luminescence intensity. The calculated results of photon emission spectra explain characteristic features of observed signal in an recent experiment. Our results indicate high functionalities of superconducting light-emitting devices.