The role of a tertiary polymer‐based additive is investigated in increasing the efficiency of inverted low bandgap polymer:fullerene bulk heterojunction (BHJ) solar cells. Charge separation in polymer BHJ solar cells relies on the phase separation between electron accepting fullerene derivatives and photoactive polymers. Proper distribution of individual phases of suitable crystallinities within the active layer is a key factor for efficient charge transport/extraction and high photovoltaic performance. Here, it is demonstrated that the minor addition of a tertiary amorphous polymer, polystyrene (PS), with optimized molecular weights can increase the overall photovoltaic efficiency of poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)]:phenyl‐C61butyric acid methyl ester (PCDTBT:PCBM) inverted BHJ solar cells, through the interfacial‐tension‐driven increase in crystallinities of photoactive phases and redistribution of PCBM molecules away from the top hole‐collecting anode interface. Complementary studies correlating polymer interfacial tension, blend internal structure, charge transport, and photovoltaic characteristics show that tertiary, high molecular‐weight polymers can serve as effective additives for improving the performance of low bandgap polymer solar cells.