The plasma rotating electrode process (PREP) is an ideal method for the preparation of metal powders such as nickel-based, titanium-based, and iron-based alloys due to its low material loss and good degree of sphericity. However, the preparation of silver alloy powder by PREP remains challenging. The low hardness of the mould casting silver alloy leads to the bending of the electrode rod when subjected to high-speed rotation during PREP. The mould casting silver electrode rod can only be used in low-speed rotation, which has a negative effect on particle refinement. This study employed continuous casting (CC) to improve the surface hardness of S800 Ag (30.30% higher than mould casting), which enables a high rotation speed of up to 37,000 revolutions per minute, and silver alloy powder with an average sphericity of 0.98 (5.56% higher than gas atomisation) and a sphericity ratio of 97.67% (36.28% higher than gas atomisation) has been successfully prepared. The dense S800 Ag was successfully fabricated by laser powder bed fusion (LPBF), which proved the feasibility of preparing high-quality powder by the “CC + PREP” method. The samples fabricated by LPBF have a Vickers hardness of up to 271.20 HV (3.66 times that of mould casting), leading to a notable enhancement in the strength of S800 Ag. In comparison to GA, the S800 Ag powder prepared by “CC + PREP” exhibits greater sphericity, a higher sphericity ratio and less satellite powder, which lays the foundation for dense LPBF S800 Ag fabrication.