Engineering energy levels of MoS2 monolayers via halide atom doping can greatly contribute to the charge kinetics and the catalytic activities.

The 2D semimetallic electrodes have been employed to show outstanding contact properties with 2D semiconducting transition‐metal dichalcogenides (TMDCs) channel, leading to large enhancement of 2D transistor and phototransistor performance. Herein, an innovative concept is established for a unique 2D semimetallic electrode‐2D TMDC channel (2D–2D) device configuration where the electronic structures of 2D semimetallic electrodes are systematically modulated to improve the contact properties with 2D monolayer molybdenum disulfide (MoS2) channel. The 2D semimetallic copper sulfide (CuS) electrodes are doped with iodine atoms by a direct exposure of iodine gas. The contact properties and charge‐transport behavior in the 2D–2D field‐effect transistors (FETs) are highly improved, which is attributed to the favorable energy band alignment and associated material properties between the iodine‐doped CuS (CuS–I) electrodes and 2D channel. The 2D–2D FETs show a high on current, high on/off ratio, and twofold improvement in mobility. Furthermore, 2D–2D phototransistors and flexible/transparent photodetectors are fabricated using the CuS–I/MoS2, which also performed outstanding photoresponsivity characteristics and mechanical durability under external bending strain conditions. These findings demonstrate a promising pathway that under the 2D–2D configuration, the electronic modulation by the iodine atoms may enable the development of future 2D electronic applications.