2D materials and their heterojunctions have been explored for gas sensing applications due to their tremendous surface-to-volume ratio, active edges with atomic thickness, and tunable electrical properties. Heterostructures of 2D materials exhibit absolutely novel physics and versatility with accelerated device performance by integrating the atomic scale properties of individual materials. Traditional gas sensors use homogeneous materials as the sensing interface in which the surface adsorbed oxygen ion species play an important role in its performance. But the performance of the sensors suffers greatly due to their selectivity and high working temperature leading to poor stability and short-term uses; the van der Waals 2D p-n heterojunction-based gas sensors hold several advantages since both the materials and the depletion layer formed at the junction can actively tune the sensing performance. By choosing 2D materials with different band structures, charge polarity, carrier concentration, and work function, band alignment at the interface can be precisely engineered to achieve the selective gas sensing performance with low operating temperature. Herein, we have reviewed the working principles, recent developments, and future perspectives of p-n heterojunctions of 2D materials for gas sensing applications. [GRAPHICS] .