AbstractThis study reports the optoelectronic characterization of few‐layer ReSe₂field effect transistors at different pressures. The output curves reveal dominant n‐type behavior and a low Schottky barrier at the metal contacts. The transfer curves show a significant hysteresis that can be exploited in memory devices with an order ofmagnitude memory window and good cycling. The devices are dramatically affected by air pressure; their conductance and mobility increase with the lowering pressure that desorbs electronegative air molecules from the surface of the material. The photoresponse under white super‐continuum laser illumination reveals that the device exhibits positive photoconductivity (PPC) at ambient and low (≈1 mbar) pressure and negative photoconductivity (NPC) in a higher vacuum (≈10⁻⁴ mbar). The transition from PPC to NPC can be explained by considering that the photoresponse is affected by molecule desorption, which yields PPC at higher pressure, and defect trapping of photogenerated carriers, which can dominate at lower pressures. The transient behavior of the device exposed to laser pulses shows a faster response and a higher photodetection efficiency at ambient pressure, with the highest signal‐to‐noise ratio at the valley of the transfer curve between p‐ and n‐type conduction.