Incorporation of solvent additive in bulk heterojunction layer has been effective method for the optimization of film morphology and crystallinity, enabling high efficiency organic solar cells under standard 1 SUN illumination. However, the effects of the additives in low-intensity indoor light environment have not been investigated much so far. In this study, a new donor polymer (PBz-ET) having an efficient spectral matching with LED was synthesized and employed. Moreover, we elucidate the different roles of additives for organic solar cell operations depending on 1 SUN and low-intensity LED illuminations. Through systemic characterizations on morphology, crystallinity, and electrical properties, we found that the additive boosting nanoscale phase separation is compatible for the organic solar cells working in 1 SUN illumination while the additive being capable of increasing crystallinity is more adaptable to those used for indoor light environment. The results in this study suggest a rational selection rule of additives for designing organic solar cells in different light environments.