Nine molecules based on benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and 2D‐BDT derivatives are studied as donor materials in organic photovoltaic (OPV) devices fabricated by thermal evaporation, aiming to understand how different alkyl lateral substituents affect the molecular packing, the charge transport, and, subsequently, the device performance. Synthesis of the molecules is followed by a comprehensive characterization using thermal and differential scanning calorimetry analyses, which confirm their thermal stability and suitability for vacuum‐processed OPV devices. Thermal analysis also demonstrates a strong correlation between the melting point reduction of the molecules and the disorder caused by the alkyl chains. As the synthesized molecules present similar optical properties, the differences in the device performance are caused by the different substituents. BDT derivatives with low melting point temperatures produce reduced current density, hole mobility, and overall device performance, which are attributed to poor molecular packing. Additionally, energy‐dispersive X‐ray spectroscopy analysis suggests phase separation with fullerene, further impacting the efficiency of the devices. The findings indicate that the photovoltaic performance of BDT‐based molecules can be modulated by avoiding aliphatic substituents, providing a strategy for the design of more efficient materials, with thermal evaporation as an ideal method to evaluate and decouple molecular packing from solubility.