To develop next-generation electronic devices, novel semiconductive materials are urgently required. The transition metal dichalcogenides (TMDs) hold the promise of next generation of semiconductor materials for emerging electronic applications. As a member of the group-10 TMDs, PdS2has a notable layer-number-dependent band structure and tremendously high carrier mobility at room temperature. Here, we demonstrate the experimental realization of centimeter-scale synthesis of the few-layer PdS2by the combination of physical vapor deposition (PVD) and chemical vapor deposition (CVD) methods. For the first time, the optical anisotropic properties of the few-layer PdS2were investigated through angle-resolved polarized Raman spectroscopy. Also, the evolution of Raman spectra was studied depending on the temperature in the range of 12–300 K. To further understand the electronic properties of the few-layer PdS2, the field-effect transistor (FET) devices were fabricated and investigated. The electronic measurements of such FET devices reveal that the PdS2materials exhibit a tunable ambipolar transport mechanism with field-effect mobility of up to ∼388 cm2V–1s–1and the on/off ratio of ∼800, which were not reported before in the literature. To well understand the experimental results, the electronic structure of PdS2was determined using density functional theory (DFT) calculations. These excellent physical properties are very helpful in developing high-performance opto-electronic applications.