This study was on the optoelectronic properties of multilayered two-dimensional MoS2 and WS2 materials on a silicon substrate using sputtering physical vapor deposition (PVD) and chemical vapor deposition (CVD) techniques. For the first time, we report ultraviolet (UV) photoresponses under air, CO2, and O2 environments at different flow rates. The electrical Hall effect measurement showed the existence of MoS2 (n-type)/Si (p-type) and WS2 (P-type)/Si (p-type) heterojunctions with a higher sheet carrier concentration of 5.50 × 105 cm−2 for WS2 thin film. The IV electrical results revealed that WS2 is more reactive than MoS2 film under different gas stimuli. WS2 film showed high stability under different bias voltages, even at zero bias voltage, due to the noticeably good carrier mobility of 29.8 × 102 cm2/V. WS2 film indicated a fast rise/decay time of 0.23/0.21 s under air while a faster response of 0.190/0.10 s under a CO2 environment was observed. Additionally, the external quantum efficiency of WS2 revealed a remarkable enhancement in the CO2 environment of 1.62 × 108 compared to MoS2 film with 6.74 × 106. According to our findings, the presence of CO2 on the surface of WS2 improves such optoelectronic properties as photocurrent gain, photoresponsivity, external quantum efficiency, and detectivity. These results indicate potential applications of WS2 as a photodetector under gas stimuli for future optoelectronic applications.