Five phosphorescent metal–anion radical coordination polymers based on a new anion radical ligand generated by in situ deprotonation of a stable zwitterionic radical are described. The N,O,N-tripodal anion radical ligand links metal cations, which leads to five isostructural coordination polymers, [M3(bipo−.)4(L)2]n (M=Cd or Mn, Hbipo−.=2,3′-biimidazo[1,2-a]pyridin-2′-one, L=Cl−, HCOO− or SCN−). The isostructural coordination polymers exhibit novel one-dimensional spirocycle-like structures. Three isostructural CdII coordination polymers display unusual phosphorescent color changes (blue, yellow, and white) induced by terminal anions. Significantly, the CdII coordination polymer with terminal Cl− possesses moderate quantum yield, and shows a bright white-light phosphorescence emission, which is independent of excitation wavelength and can even be excited by visible light. Upon adjusting the metal cation to MnII, two isostructural MnII coordination polymers reveal deep-blue-light phosphorescence emissions that are independent of terminal anions. As radical-based coordination polymers, some of them show antiferromagnetic interactions between radical species or radical and metal center.