The study investigates the two different underlying ablation mechanisms of WS2 processed by femtosecond (fs) laser with different fluences. With increasing fluence, the saturable expansion of craters and the transformation of three distinct crater morphologies are found. The material response and the transfer and deposition of laser energy are tracked by using a plasma model based on the classical single rate equation model and the Drude model. The results of the numerical simulation and time-resolved transient reflectivity reveal the two different ablation mechanisms, which are coulomb explosion and phase explosion. The mechanism of material removal is distinguished by the critical threshold of 0.85 J/cm2. In addition, the internal ablation region exhibits a high concentration of defects and WO3 according to the results of Raman spectra, X-ray photoelectron spectra, and morphology-dependent photoluminescence mapping. Due to the high concentration with high fluence, the device of WS2/Si p-n junction exhibits a 2.6 times enhancement on the current under forward bias. The findings would be of value to engineer structures to tailor the optoelectronic response of WS2 and to develop potential future optoelectronic devices.