Based on different benzenecarboxylic acids (H3BTC = 1,3,5-benzenetricarboxylic acid; H4BTEC = 1,2,4,5-benzenetetracarboxylic acid; m-H3BTC = 1,2,4-benzenetricarboxylic acid) and viologen cations (BV2+ = 1,1′-bis(butyl)-4,4′-bipyridinium dication; AV2+ = 1,1′-bis(amyl)-4,4′-bipyridinium dication; HV2+ = 1,1′-bis(hexyl)-4,4′-bipyridinium dication), five novel supramolecular assemblies (BV)(H2BTC)2(H3BTC)2 (1), [(BV)0.5(H3BTEC)]·H2O (2), (BV)0.5(m-H2BTC) (3), (AV)0.5(m-H2BTC) (4), (HV)0.5(m-H2BTC) (5) have been prepared. The electron-deficient viologen groups and the electron-donating benzenecarboxylate units are hydrogen-bonded to form the donor-acceptor (D–A) system. Under light illumination, photoactivated electrons can be transferred from the donor to the acceptor units in compounds 2–5. Their different photoactive properties can be attributed to the alkyl groups introduced, packing and valence of the functional D–A moieties.