applications, the development of a sensor with exceptional energy efficiency is a requisite. [1,7,8] However, conventional electrical sensors based on resistors or diodes inevitably require the external application of a constant voltage (or current) to output an electrical signal, and thus consume electric power (current times voltage) for the operation. [3,9] In addition, many gas sensors based on metal oxide semiconductors and inorganic nanomaterials require additional thermal energy in the range of 200-500 °C to activate and optimize surface absorption and desorption of gas molecules on the sensing surface. [10][11][12] Power consumption and heating will become increasingly problematic as the number of connected devices increases in highly networked system. Therefore, these external voltage sources and heating elements, required for device operation, are ultimately undesirable with respect to low power consumption, long-term stability, and miniaturization. To address these issues, the development of a new class of sensor platforms capable of consuming minimal steady-state power is necessary.Atomically thin 2D materials, including semimetallic graphene (Gr) and semiconducting transition metal dichalcogenides, have great potential in chemical sensors with excellent sensitivity due to their large surface-to-volume ratio and superior electrical properties. [13][14][15] In addition, combined with the recent advent of artificial van der Waals heterostructures constructed by staking various 2D materials in a designed manner, the ability to tune the electrochemical potential of each constituent layer and the built-in potential of the heterostructures by electrical and/or chemical means enables us to design hybrid heterostructures based on 2D materials with unconventional functions for various device applications. [16][17][18][19][20][21][22] Such unique capability of 2D hybrid heterostructures may provide an unexplored strategy to realize a chemical sensor with extremely low power consumption as well as high sensitivity. Nevertheless, the chemical sensing based on 2D material heterostructures has rarely been demonstrated yet. [23,24] In this work, we propose a device concept for self-powered chemical sensing driven by chemical-responsive photovoltaic action in the Gr-based heterojunction devices. We also prove a Ultralow power chemical sensing is essential toward realizing the Internet of Things. However, electrically driven sensors must consume power to generate an electrical readout. Here, a different class of self-powered chemical sensing platform based on unconventional photovoltaic heterojunctions consisting of a top graphene (Gr) layer in contact with underlying photoactive semiconductors including bulk silicon and layered transition metal dichalcogenides is proposed. Owing to the chemically tunable electrochemical potential of Gr, the built-in potential at the junction is effectively modulated by absorbed gas molecules in a predictable manner depending on their redox characteristics. Such ability distinctive fr...