Bulk heterojunction (BHJ) organic photovoltaic (OPV) promise low cost solar energy and have caused an explosive increase in investigations during the last decade. Control over the 3D morphology of BHJ blend films in various length scales is one of the pillars accounting for the significant advance of OPV performance recently. In this contribution, we focus on the strategy of incorporating an additive into BHJ blend films as a morphological control agent, i.e., ternary blend system. This strategy has shown to be effective in tailoring the morphology of BHJ through different inter-and intra-molecular interactions. We systematically review the morphological observations and associated mechanisms with respect to various kinds of additives, i.e., polymers, small molecules and inorganic nanoparticles. We organize the effects of morphological control (compatibilization, stabilization, etc.) and provide general guidelines for rational molecular design for additives toward high efficiency and high stability organic solar cells.

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