The growth of high-quality organic single crystals with controlled size is crucial to both the study of the fundamental physical properties of the materials, and to their practical utilization. Here, a novel gas–liquid interface technique is presented for the growth of anthracene (AN) and its doped single crystals. The AN single crystals showed sheet shape, large size of up to centimeter range, and neat surface morphology. The results of X-ray diffraction and optical measurements indicated that such laminated films exhibited higher crystalline quality and photoluminescence (PL) efficiency than those obtained by physical vapor transport (PVT) method or original solution growth (SG) method. The crystal formation process is explored by quoting the principle of Langmuir–Blodgett film and the terrace–ledge–kink crystal growth model. Such a crystal growth technique can be expanded to the gas–liquid–solid interface to directly grow AN single crystals on electrodes (such as silicon wafer and golden substrate), which may be valuable for the preparation of organic single crystal based devices including light-emitting diodes and field effect transistors.