High-crystalline DBTTF-TCNQ charge-transfer complex crystals with larger grains visible even by an optical microscope have been successfully grown, assisted by ionic liquid (IL) in vacuum co-deposition. Although the charge transfer reaction between the DBTTF and TCNQ molecules was ready to occur to form the complex regardless of the presence or absence of the IL even at room temperature, the subsequent crystal growth of the DBTTF-TCNQ complexes was enhanced by the IL, especially much more at temperatures higher than room temperature, leading to a significant improvement in the crystallinity of the complexes. The crystal growth mechanism of the DBTTF-TCNQ complexes in the IL was discussed based on the results of in situ optical microscope observation during the deposition of the DBTTF and TCNQ molecules into the IL. (C) 2016 Elsevier B.V. All rights reserved.