The delocalization length of charge carriers in organic semiconductors influences their mobility and is an important factor in the design of functional materials. Here, we have studied the radical anions of a series of linear and cyclic butadiyne-linked porphyrin oligomers using CW-EPR, 1H Mims ENDOR and NIR/MIR spectroelectrochemistry together with DFT calculations and multiscale molecular modeling. Low-temperature hyperfine EPR spectroscopy and optical data show that polarons are delocalized nonuniformly over about four porphyrins with most of the spin density on just two units even in the cyclic structures, in which all porphyrin sites are identical. Room temperature CW-EPR spectra indicate a larger spatial distribution of spin density on the EPR time scale. We introduce a combined molecular dynamics simulations and DFT approach to demonstrate that dynamic migration of delocalized polarons can occur in porphyrin oligomers and that this fully accounts for the apparent spin density distribution at room temperature. This method is a powerful tool in both the study and development of molecular wires and molecular electronics.