Two organic polymers containing alternating electron donating triarylamine and electron accepting thiazolo[5,4-d]thiazole (TzTz) moieties have been synthesized and their redox states investigated. When donor and acceptor units are proximal (polymer 1), electron density is delocalized, leading to a small electrical and optical band gap; these are larger with the inclusion of an adjoining alkynyl-phenyl bridge (polymer 2), where electron density is more localized due to the rotation of the monomer units. As a result, 1 and 2 display different optical and fluorescence properties in their neutral states. Upon chemical and electrochemical redox reactions, radicals form in both 1 and 2, yielding magnetic materials that display temperature independent paramagnetism, attributable to delocalization of radical spins along the polymeric backbones. The ability to convert between diamagnetic and paramagnetic states upon chemical oxidation and/or reduction allows for the materials to display switchable magnetism and fluorescence, imparting multifunctionality to these solid-state purely organic materials.