Diketopyrrolopyrrole (DPP) is a component of a large number of materials used for optoelectronic applications. As it is exclusively used in combination with aromatic donors, the properties of its homopolymers are unknown. Because donor–acceptor character has been shown for other systems to reduce bandwidths, DPP homopolymers should have even larger conduction bands and better n-type conductivity than the thiophene-flanked systems, which have exceptional n-type conductivity and ambipolar character. Therefore, a theoretical study was carried out to elucidate the properties of the unknown DPP homopolymer. Calculations were done with density functional theory and with the complete active space self-consistent field method plus n-electron valence state perturbation theory for the dynamic correlation. Poly-DPP is predicted to have radical character and an extremely wide low-lying conduction band. If it were possible to produce this material, it should have unprecedented n-type conductivity and might be a synthetic metal. A comparison with various unknown donor–acceptor systems containing vinyl groups and thienyl rings with a higher concentration of DPP than the known copolymers reveals how donor–acceptor substitution reduces bandwidths and decreases electron affinities.