||Charge-transfer complexes (CTs) have been studied for several decades as a result of the unique chemical and physical properties. More in-depth study of this concept and its application in conjunction with other organic CTs may provide a solution for one of the most difficult bottlenecks in organic device research. Further progress is necessary in several areas. First, only a limited crystallinity is available relating the structure of CTs to their properties. Further analysis of donor–acceptor (D-A) overlap, stacking structure, and degree of charge transfer between the D and A molecules could yield much insight into the structure–function relationship of these materials and a rational design of CTs with electrical properties ranging from insulating to metallic. Herein, we report an approach to fabricate organic CTs of high crystallinity by eutectic crystallization. Our method shows the simple process and crystal growth of improve crystallinity with combined soft-lithography.