A small donor–acceptor molecule is synthesized in a two-step procedure involving reaction of N,N-diphenylhydrazine on 2,5-diformylthiophene and Knoevenagel condensation. Results of UV/Vis absorption spectroscopy and cyclic voltammetry show that replacement of the phenyl ring bridge of a reference compound 2 by an azo group produces a slight red-shift of λmax, an enhancement of the molecular absorption coefficient, and a decrease of the energy level of the frontier orbitals. A preliminary evaluation of the potentialities of compound 1 as donor material in a basic bilayer planar heterojunction cell of 28 mm2 active area using C60 as acceptor gave a short-circuit current density of 6.32 mA cm−2 and a power conversion efficiency of 2.07 %.