The invention discloses a nano-scale low-valent ion composite doped gamma-Ce2S3 red pigment, wherein the ion valence of the doped ion M is 2, at least two kinds of the doped ions exist, a molar ratioof Ce<3+> to M[total] is 2(1-x):3x, and x is more than 0 and is less than or equal to 0.1. The invention further discloses a preparation method of the nano-scale low-valent ion composite doped gamma-Ce2S3 red pigment. According to the present invention, the composite doped low-valent ions enter the gamma-Ce2S3 crystal lattice, and the doping is achieved by replacing the Ce<3+> ions and filling thecation vacancy in the crystal lattice, such that the gamma-Ce2S3 crystal lattice is effectively stabilized, and the high-temperature stability of the pigment is substantially improved so as to substantially expand the application of the material under the high temperature condition; and the preparation method has advantages of simple process, easy operation, easy control of influence factors, lowproduction cost, and easy promotion and application.