Highly dispersive molybdenum disulfide nanoflakes (MoS2 NFs), without any phase transition during the exfoliation process, are desirable for full utilization of their semiconductor properties in practical applications. Here, we demonstrate an innovate approach for fabricating MoS2 NFs by using hydrazine-assisted ball milling via the synergetic effect of chemical intercalation and mechanical exfoliation. The NFs obtained have a lateral size of 600–800 nm, a thickness less than 3 nm, and high crystallinity in the 2H semiconducting phase. They form a stable dispersion in various solvents, which will be helpful for many applications, due to the oxygen functional group. To investigate production of a two-dimensional (2D) photodetector, 2D semiconducting MoS2, MoS2–p-Si vertical devices were fabricated, and their optical properties were characterized. The photodiode exhibited consistent responses with excellent photo-switching characteristics with wavelengths of 850, 530, and 400 nm