the complex microstructures and undesir able qualities of conventional organic bulk thin films can largely lead to severe performance bottlenecks in functional OFETs [23,24] and serve as essential chal lenges in unveiling the intrinsic electrical properties. [25] Therefore, a new organic material is profoundly required to satisfy the anticipated demand for fundamental studies and to sustain the revolutionary advancement in organic electronics.As an emerging electronic material, 2D molecular crystals (2DMCs) have attracted particular attention since their discovery. [26,27] The material structure of 2DMC features a monolayer (ML) or few layers of molecules that are assembled via weak van der Waals (vDW) bonding along two dimensions. 2DMCs have also dem onstrated unique characteristics of thick ness uniformity over a large scale, perfect lateral continuity with an atomically flat surface, and longrange molecular ordering. Particularly, when the available conforma tions of crystalline molecular semiconductors are restricted under a special constraint geometry, the interlayer screening that commonly exists in the 3D bulk organic semiconducting crystals can be effectively eliminated. [27,28] Thus, 2DMCs are extremely fascinating for the direct exploration of the charge accumulation and transport behaviors regarding the properties of the semiconductor/insulator interface, disorder effects, and polaronic relaxation. Especially, in 2DMCbased FETs, the inter facial interactions on the molecular crystals can be well con fined at 2D limit, exhibiting different influences from layer to layer. Thus, the microscopic behaviors of charge carriers can be much effectively modulated. Therefore, 2DMCs possess unique optoelectronic properties that cannot be achieved in conven tional bulk molecular crystals. [29][30][31] Besides, utilizing their ultrathin structural features and superior interface qualities can significantly contribute to the enhanced performance of 2DMC based functional FETs. These unique merits, combined with intrinsic properties, such as lightweight construction, material versatility, and chemical/environment stability, explicitly enable these 2D crystals fascinating prospects for realistic applications in advanced electronic technologies. [15,[32][33][34][35] Obtaining molecular crystals with 2D morphology is an essential prerequisite for scientific and technological studies. Pioneering efforts have been devoted to vaporgrown 2DMCs. [36][37][38][39][40][41][42] However, the expensive preparation cost and rigorous growth conditions have rendered these methods Based on intensive research, organic field-effect transistors (OFETs) will likely remain at the zenith in information science for many years due to their numerous potential applications in portable and smart electronic devices. Elucidating the intrinsic charge-transport behavior and realizing functional OFETs with superior device characteristics have been the cornerstones for the sustainable advancement in organic electronics. The emerging 2D molecular crystal...