Building on our previous works that compared the efficacy of terpolymers vs. ternary blends in improving the performance of bulk heterojunction organic solar cells, the final piece of this series of studies focuses on comparing terpolymer and ternary blends constructed with two polymers with structurally similar backbones (monoCNTAZ and FTAZ) yet markedly different open circuit voltage (Voc) values. Terpolymers and ternary blends of five different ratios were studied and the results demonstrate that while the overall performance of both the systems is similar, the ternary blends exhibit higher short circuit current (Jsc) values, while the terpolymers exhibit higher Voc values. Investigation of the charge transfer state using low-energy external quantum efficiency (EQE) indicates that the ternary blends are governed by a parallel-like mechanism, while the terpolymer does not follow this mechanism. The key morphological difference between the systems, as elucidated by resonance soft X-ray scattering (RSoXS), is the slightly smaller size (∼60 nm) of domains in the ternary blends compared to that of the terpolymer (∼80 nm), which may affect exciton harvesting in the terpolymer system and lead to lower Jsc values. In addition, a lower driving force for the formation of charge transfer (CT) state is also likely to contribute to the lower Jsc values in the terpolymer system. All together, the data show that structurally similar (perhaps even miscible) polymers still exhibit key differences in performance when paired in terpolymers vs. ternary blends and allow us to further illuminate the underlying mechanisms of such complex systems.