Three conjugated triphenylamine-based poly(azomethine)s were prepared via well-known polycondensation chemistry using cheap and readily available starting materials and the results were contrasted with rrP3HT. Three functionalized diaminetriphenylamines (TPA(X), X ¼ –H, –OMe, –CN) were polymerized in a simple one-step process with 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarbaldehyde (ThOx), with water being the only side product. The resulting polymers (TPA(X)ThOx, X ¼ –H, –OMe, –CN) were characterized by GPC, IR and NMR, and show a good thermal stability. The opto-electronic properties could be tuned by changing the functionalization (X ¼ –H, –OMe, –CN) on the triphenylamine moiety. Photovoltaic devices based on TPA(X)ThOx/PCBM (1 : 2) showed power conversion efficiencies in the range of 0.02–0.04%. TRMC measurements showed that the presence of PCBM as an electron acceptor facilitates the formation of free mobile charges after excitation of the polymer. The low device efficiencies are attributed to a low hole-mobility of the polymer in combination with poor active layer morphology.