The all-(E)-configured tetrastilbenylmethanes 3a−e and 5a,b can be obtained by fourfold Wittig−Horner reactions. The tetrahedral arrangement of these compounds guarantees independent stilbenoid chromophores with a high chromophore density. Apart from (E)/(Z) isomerization reactions, irradiation leads to a three-dimensional network with isolated unchanged stilbene units. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)