Materials based on the laminar ordering of self-assembled molecules have a unique potential for applications requiring efficient energy migration through densely packed chromophores. Here, employing molecular assemblies of coil–rod–coil block molecules for triplet–triplet annihilation upconversion (TTA-UC) based on triplet energy migration with linearly polarized emission is reported. By covalently attaching discrete-length oligodimethylsiloxane (oDMS) to 9,10-diphenylanthracene (DPA), highly ordered 2D crystalline DPA sheets separated by oDMS layers are obtained. Transparent films of this material doped with small amounts of triplet sensitizer PtII octaethylporphyrin show air-stable TTA-UC under non-coherent excitation. Upon annealing, an increase in TTA-UC up to two orders of magnitude is observed originating from both an improved molecular ordering of DPA and an increased dispersion of the sensitizer. The molecular alignment in millimeter-sized domains leads to upconverted linearly polarized emission without alignment layers. By using a novel technique, upconversion imaging microscopy, the TTA-UC intensity is spatially resolved on a micrometer scale to visually demonstrate the importance of molecular dispersion of sensitizer molecules for efficient TTA-UC. The reported results are promising for anti-counterfeiting and 3D night-vision applications, but also exemplify the potential of discrete oligodimethylsiloxane functionalized chromophores for highly aligned and densely packed molecular materials.