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Abstract Conjugated polymers (CPs) play a central role in electronic applications due to their easily tuned electronic and ionic conductivities via chemical or electrochemical doping. Although doping improves charge conduction by introducing high densities of carriers into the CP, the accompanying structural changes and their impact on carrier mobility remain elusive. Methods capable of probing carrier distributions and their dependence on polymer morphology are needed to better understand how to improve conductivity. Here, a transient absorption (TA) spectroscopy approach is demonstrated, capable of directly probing mobile and trapped carriers in doped CPs and that is also sensitive to polymer nanostructure by using a model polythiophene system with tuned crystallinity. Exciting polarons in the polymer films produces distinct photoinduced absorption signals in the near‐infrared spectrum that decay during the picosecond timescale in the form of biphasic, stretched exponential kinetics, which reflect a distribution of mobile (free) and trapped polarons. The kinetic analysis provides evidence for mobile polarons irrespective of polymer film crystallinity, whereas polarons located in impure amorphous phases with reduced chain ordering exist within a deeper distribution of trap states. Altogether, these observations suggest a stronger correlation of carrier trapping with local chain ordering (planarity or aggregation) rather than polymer crystallinity.