Lithium argyrodite solid electrolytes have attracted ever-increasing attention for all-solid-state batteries due to their high ionic conductivity and low cost. However, the relation between structure and ionic transport for the halogen-rich lithium argyrodites under different synthesis routes is still elusive. Herein, the influence of synthesis procedures, such as annealing conditions and balling milling, on the structure, ionic conductivity, and activation energy of the lithium argyrodite (e.g., Li_5.5PS_4.5Cl_1.5, Li_5.3PS_4.3Cl_1.7), is systematically investigated. Compared with high-energy ball milling followed by annealing, using fast dry mixing followed by annealing can obtain comparable ionic conductivity of the chlorine-rich lithium argyrodites. Single-crystal LiNi_0.83Co_0.11Mn_0.06O₂-based solid-state battery with these electrolytes shows stable cycling performance, demonstrating that chlorine-rich lithium argyrodite is a promising candidate for all-solid-state batteries.