Solid-state argyrodite electrolytes are promising candidate materials to produce safe all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity. These batteries can be used to power electric vehicles and portable consumer electronics which need high power density. Atomic-scale modeling with ab initio calculations became an invaluable tool to better understand the intrinsic properties and stability of these materials. It is also used to create new structures to tailor their properties. This review article presents some of the recent theoretical investigations based on atomic-scale modeling to study argyrodite electrolytes for ASSLBs. A comparison of the effectiveness of argyrodite materials used for ASSLBs and the underlying advantages and disadvantages of the argyrodite materials are also presented in this article.