The negative photoconductivity (NPC) effect originating from the surface shell layer has been considered as an efficient approach to improve the performance of optoelectronic nanodevices. However, a scientific design and precise growth of NPC-effect-caused shell during nanowire (NW) growth process for achieving high-performance photodetectors are still lacking. In this work, GeS NWs with a controlled sulfur-rich shell, diameter, and length are successfully prepared by a simple chemical vapor deposition method. As checked by transmission electron microscopy, the thickness of the sulfur-rich shell ranges from 10.5 ± 1.5 to 13.4 ± 2.5 nm by controlling the NW growth time. The composition of the sulfur-rich shell is studied by X-ray photoelectron spectroscopy, showing the decrease of S in the GeSx shell from the surface to core. When configured into the well-known phototransistor, a featured NPC effect is observed, benefiting the high-performance photodetector with high responsivity of 105 A·W-1 and detectivity of 1012 Jones for λ = 405 nm with ultralow intensity of 0.04 mW·cm-2. However, the thicker-shell NW phototransistor shows an unstable photodetector behavior with smaller negative photocurrent because of more hole-trapping states in the thicker shell. All results suggest a careful design and controlled growth of an NPC-effect-caused shell for future optoelectronic applications.