The three-component reaction of aryl boronic acids with 1,2,4,5-tetrahydroxybenzene and 1,2-bis(4-pyridyl)ethylene or 4,4-bipyridine leads to the formation of dark-purple boronate ester polymers. Crystallographic analyses show that the polymer strands have a zig-zag geometry, and the bis(dioxaborole) units are connected by dipyridyl linkers through dative B-N interactions. Upon dissolution of the polymers in hot chloroform, most of the B-N connections are broken, which indicates that polymer formation is a reversible process. A computational study provides evidence that the strong color of the polymers is due to efficient intrastrand charge-transfer excitations from the tetraoxobenzene to the dipyridyl linker.