AbstractThe coupling of different two‐dimensional materials (2DMs) to form van der Waals heterostructures (vdWHs) is a powerful strategy for adjusting the electronic properties of 2D semiconductors, for applications in opto‐electronics and quantum computing. 2D molybdenum disulfide (MoS2) represents an archetypical semiconducting, monolayer thick versatile platform for the generation of hybrid vdWH with tunable charge transport characteristics through its interfacing with molecules and assemblies thereof. However, the physisorption of (macro)molecules on 2D MoS2 yields hybrids possessing a limited thermal stability, thereby jeopardizing their technological applications. Herein, we report the rational design and optimized synthesis of 2D covalent organic frameworks (2D‐COFs) for the generation of MoS2 / 2D‐COF vdWHs exhibiting strong interlayer coupling effects. The high crystallinity of the 2D‐COF films made it possible to engineer an ultrastable periodic doping effect on MoS2, boosting devices’ field‐effect mobility at room temperature. Such a performance increase can be attributed to the synergistic effect of the efficient interfacial electron transfer process and the pronounced suppression of MoS2’s lattice vibration. This proof‐of‐concept work validates an unprecedented approach for the efficient modulation of the electronic properties of 2D transition metal dichalcogenides toward high‐performance (opto)electronics for CMOS digital circuits.This article is protected by copyright. All rights reserved