A combination of theory and experiment is used to identify a novel variable excitonic coupling in a series of building blocks for small phenylacetylene dendrons. Systematic changes in the experimental emission spectra, radiative lifetimes, and polarization anisotropies as the number of meta-conjugated branches increases provide evidence for a qualitative change in the electronic structure in the relaxed excited state. The excited state electronic structure is investigated theoretically using ab initio CASSCF and CASPT2 calculations, which indicate the presence of large electronic coupling in the emitting geometry that is not seen for the absorbing geometry of the same molecules. The changes in electronic structure that occur upon excited-state relaxation can be understood in terms of a variable excitonic coupling between the phenylactylene branches, which takes these molecules from the weak coupling to the strong coupling regime as they relax on the excited state. The origin of this geometry-dependent coupling is investigated through the interpretation of ab initio calculations in terms of Forster, Dexter, and through-bond charge-transfer interactions. We find that the change in the coupling arises primarily from an increase in the through-bond or charge-transfer component of the coupling, despite the absence of large changes in charge distribution. A theoretical comparison of meta-versus para-substituted phenylacetylenes clarifies why this effect is so pronounced in the meta-substituted molecules.