Radical‐initiated difunctionalization of alkenes is one of the most important methods in organic synthesis and medicinal chemistry, which can be applied to synthesize value complex compounds as well as structural motifs that found in bioactive natural products and pharmaceuticals. In recent years, impressive progress have been made in this area with ideal silver catalysis. Here, we summarize recent advances in silver‐mediated radical difunctionalization of alkenes for the formation of diverse bonds, including 1) two‐component radical difunctionalization reactions enabled by an intramolecular cyclization process toward various cyclic compounds and 2) three‐component radical difunctionalization reactions leading to complex linear compounds. These silver‐mediated radical alkene difunctionalization transformations are general initiated by different radicals, such as carbon‐, oxygen‐, sulfur‐, phosphinyl‐, and halogen‐center radicals, followed by terminated with nucleophiles to form two new bonds in a single reaction. Ag catalysis: Recent advances in the silver‐mediated intermolecular radical 1,2‐difunctionalization of alkenes are summarized. These reaction are classified by the substrate type and radical regents. Two new C−C/C−C bonds, C−C/C−X bonds (X=F, O, S…) and C−X/C−X bonds (X=O, Br, I…) could be constructed in a single reaction.