A majority of conjugated organic polymers are electron-rich materials, with far fewer electron-poor (i.e., electron accepting) analogues. Here we report the synthesis and preliminary characterization of new class of electron-poor poly(arylene ethynylene)s (PAEs) that contain 5,8-quinoxaline ethynylene repeat units. While various PAE copolymers consisting of alternating electron-rich and electron-poor units display lower bandgaps than poly(phenylene ethynylene)s, the poly(5,8-quinoxaline ethynylene) (PQE) reported in this study has a higher electron affinity and lower bandgap (2.25 eV) than many of these donor–acceptor materials. In comparison to poly(5,8-quinoxaline)s (PQs), which do not have an ethynylene linkage between the quinoxalines, the PQE has a red-shifted absorption spectrum that is consistent with a more highly conjugated and planar backbone. In addition, the PQE has a lower electrochemical reduction potential than both a corresponding PQ and a donor–acceptor alternating PAE copolymer that contains the quinoxaline unit as the electron-poor component.