An important challenge when developing materials for triplet–triplet annihilation upconversion (TTA-UC) is achieving efficient and well-functioning solid-state systems. We here explore the effect of intramolecular TTA in oligomers and dendrimers based on the 9,10-diphenylanthracene (DPA) chromophore. The macromolecules are sensitized using palladium porphyrin, both in solution and in solid poly(methyl methacrylate) (PMMA), demonstrating a positive effect on overall upconversion in the solid state correlating with the well-controlled size of the DPA constructs. The UC kinetics is modeled and fit to steady-state and time-resolved emission data to give further insight into the intramolecular excited-state migration and annihilation in the macromolecular annihilator systems.