The research for efficient organic materials organized in bulk heterojunction (BHJ) thin films for organic photovoltaics (OPVs) has shown a significant breakthrough in the past decade. Desired structural organization can be attained through various strategies. In this regard, the current review highlights tuning of alkyl chains introduced on molecular structures of active materials. The recent wide literature is classified based on the introduction of alkyl chains on polymers and small molecules used as donor and acceptor materials. The design of these materials, the morphological aspects of the active layers, and the performances of the related photovoltaic cells are detailed. A comprehensive discussion on chemical structures of the different material families considered, their modification by alkyl chains of various natures, and the morphological aspects are reported and tabulated.