Herein, we reported a unique photo device consisting of monolayer graphene and a few-layer rhenium diselenide (ReSe2) heterojunction. The prepared Gr/ReSe2-HS demonstrated an excellent mobility of 380 cm2/Vs, current on/off ratio ~ 104, photoresponsivity (R ~ 74 AW-1 @ 82 mW cm-2), detectivity (D* ~ 1.25 × 1011 Jones), external quantum efficiency (EQE ~ 173%) and rapid photoresponse (rise/fall time ~ 75/3 µs) significantly higher to an individual ReSe2 device (mobility = 36 cm2 V-1s-1, Ion/Ioff ratio = 1.4 × 105-1.8 × 105, R = 11.2 AW-1, D* = 1.02 × 1010, EQE ~ 26.1%, rise/fall time = 2.37/5.03 s). Additionally, gate-bias dependent Schottky barrier height (SBH) estimation for individual ReSe2 (45 meV at Vbg = 40 V) and Gr/ReSe2-HS (9.02 meV at Vbg = 40 V) revealed a low value for the heterostructure, confirming dry transfer technique to be successful in fabricating an interfacial defects-free junction. In addition, HS is fully capable to demonstrate an excellent gas sensing response with rapid response/recovery time (39/126 s for NO2 at 200 ppb) and is operational at room temperature (26.85 °C). The proposed Gr/ReSe2-HS is capable of demonstrating excellent electro-optical, as well as gas sensing, performance simultaneously and, therefore, can be used as a building block to fabricate next-generation photodetectors and gas sensors.